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.

Structural characterisation of reaction zone for friction stir welded aluminium-stainless steel joint

In the present investigation, commercially pure Al has been joined with 304 stainless steel (SS) by friction stir welding. The assembly finds widespread application in the field of cryogenics, nuclear, structural industries and domestic appliances. Microstructural characterisation was carried out using scanning and transmission electron microscopes. It has been found that diffusion of Fe, Cr and Ni is substantial within Al; however, diffusion of Al within 304SS is limited. Owing to interdiffusion of chemical species across the bondline, discrete islands of Fe3Al intermetallic form within the reaction zone. The rubbing action of tool over the butting edge of 304SS removed fine particles from 304SS, which were embedded in the stirring zone of Al matrix. Subsequently, austenite underwent phase transformation to ferrite due to large strain within this grain. Fracture path mainly moves through stirring zone of Al alloy under tensile loading; however, in some places, presence of Fe3Al compound has been also found.

Structural, vibrational and thermal studies of a new nonlinear optical material: L-Asparagine-L-tartaric acid

Crystals of a new nonlinear optical (NLO) material, viz., L-asparagine-L-tartaric acid (LALT)(1) were grown by slow evaporation of an aqueous solution containing equimolar concentrations of L-asparagine and t-tartaric acid. The structure of the title compound which crystallizes in the non-centrosymmetric monoclinic space group P2(1) consists of a molecule of L-asparagine and a molecule of free L-tartaric acid both of which are interlinked by three varieties of H-bonding interactions namely O-H center dot center dot center dot O, N-H center dot center dot center dot O and C-H center dot center dot center dot O. The UV-Vis-NIR spectrum of 1 reveals its transparent nature while the vibrational spectra confirm the presence of the functional groups in 1. The thermal stability and second harmonic generation (SHG) conversion efficiency of 1 were investigated. (C) 2012 Elsevier B.V. All rights reserved.

Structural, EPR, photo and thermoluminescence properties of ZnO:Fe nanoparticles

Zn(1-x)Fe(x)O(1+0.5x) (x = 0.5-5 mol%) nanoparticles were synthesized by a low temperature solution combustion route. The structural characterization of these nanoparticles by PXRD, SEM and TEM confirmed the phase purity of the samples and indicated a reduction in the particle size with increase in Fe content. A small increase in micro strain in the Fe doped nanocrystals is observed from W-H plots. EPR spectrum exhibits an intense resonance signal with effective g values at g approximate to 2.0 with a sextet hyperfine structure (hfs) besides a weak signal at g approximate to 4.13. The signal at g approximate to 2.0 with a sextet hyperfine structure might be due to manganese impurity where as the resonance signal at g approximate to 4.13 is due to iron. The optical band gap E-g was found to decrease with increase of Fe content. Raman spectra exhibit two non-polar optical phonon (E-2) modes at low and high frequencies at 100 and 435 cm(-1) in Fe doped samples. These modes broaden and disappear with increase of Fe do pant concentration. TL measurements of gamma-irradiated (1-5 kGy) samples show a main glow peak at 368 degrees C at a warming rate of 6.7 degrees Cs-1. The thermal activation parameters were estimated from Glow peak shape method. The average activation energy was found to be in the range 0.34-2.81 eV. (C) 2012 Elsevier B.V. All rights reserved.

Relaxor Ferroelectric Behavior and Structural Aspects of SrNaBi2Nb3O12 Ceramics

The SrNaBi2Nb3O12 (SNBN) powder was prepared via the conventional solid-state reaction method. X-ray structural studies confirmed the phase to be a three-layered member of the Aurivillius family of oxides. The SNBN ceramics exhibited the typical characteristics of relaxor ferroelectrics, associated with broad and dispersive dielectric maxima. The variation of temperature of dielectric maxima (T-m) with frequency obeyed the Vogel-Fulcher relationship. Relaxor behavior was believed to be arising from the cationic disorder at A-site. Pinched ferroelectric hysteresis loops were observed well above T-m.

Residual strength evaluation of concrete structural components under fatigue loading

This paper presents methodologies for residual strength evaluation of concrete structural components using linear elastic and nonlinear fracture mechanics principles. The effect of cohesive forces due to aggregate bridging has been represented mathematically by employing tension softening models. Various tension softening models such as linear, bilinear, trilinear, exponential and power curve have been described with appropriate expressions. These models have been validated by predicting the remaining life of concrete structural components and comparing with the corresponding experimental values available in the literature. It is observed that the predicted remaining life by using power model and modified bi-linear model is in good agreement with the corresponding experimental values. Residual strength has also been predicted using these tension softening models and observed that the predicted residual strength is in good agreement with the corresponding analytical values in the literature. In general, it is observed that the variation of predicted residual moment with the chosen tension softening model follows the similar trend as in the case of remaining life. Linear model predicts large residual moments followed by trilinear, bilinear and power models.

Effect of Grain Size on Structural and Magnetic Properties of CuFe2O4 Nanograins Synthesized by Chemical Co-Precipitation

CuFe2O4 nanograins have been prepared by the chemical co-precipitation technique and calcined in the temperature range of 200-1200 degrees C for 3 h. A wide range of grain sizes has been observed in this sintering temperature range, which has been determined to be 4 to 56 nm. Formation of ferrite has also been confirmed by FTIR measurement through the presence of wide band near 600 and 430 cm(-1) for the samples in the as-dried condition. Systematic variation of wave number has been observed with the variation of the calcination temperature. B-H loops exhibit transition from superparamagnetic to ferrimagnetic state above the calcination temperature of 900 degrees C. Coercivity of the samples at lower calcination temperature of 900 degrees C reduces significantly and tends towards zero coercivity, which is suggestive of superparamagnetic transition for the samples sintered below this temperature. Frequency spectrum of the real and imaginary part of complex initial permeability have been measured for the samples calcined at different temperature, which shows wide range of frequency stability. Curie temperature, T-c has been measured from temperature dependence initial permeability at a fixed frequency of 100 kHz. Although there is small variation of T-c with sintering temperature, the reduction of permeability with temperature drastically reduce for lower sintering temperature, which is in conformity with the change of B-H loops with the variation of sintering temperatures.

Swift heavy ion induced structural, iono and photoluminescence properties of beta-CaSiO3:Dy3+ nanophosphor

CaSiO3:Dy3+ (1-5 mol%) nanophosphors have been prepared by a low temperature solution combustion method. The structural and luminescence (ionoluminescence; IL and photoluminescence; PL) studies have been carried out for pristine and ion irradiated samples. The XRD patterns of pristine sample show a prominent peak at (320) for the monoclinic structure of beta-CaSiO3. Upon ion irradiation, the intensity of the prominent peak is decreased at the fluence of 7.81 x 10(12) ions cm(-2) and at higher fluence of 15.62 x 10(12) ions cm(-2), the prominent peak completely vanishes. The decrease in peak intensity might be due to the stress induced point defects. On-line IL and in situ PL studies have been carried out on pelletized samples bombarded with 100 MeV Si7+ ions with fluences in the range (7.81-15.62) x 10(12) ions cm(-2). The characteristic emission peaks at 481,574, 664 and 754 nm recorded in both IL and PL are attributed to the luminescence centers activated by Dy3+ ions. It is found that IL and PL emissions intensity decreases with increase in Si7+ ion fluence. The decrease in intensity can be due to the destruction of Si-O-Si and O-Si-O type species present on the surface of the sample. FTIR studies also confirm the Si-O-Si and O-Si-O type species observed to be sensitive for swift heavy ion (SHI) irradiated samples. (C) 2012 Elsevier B.V. All rights reserved.

Unusual co-crystal of isonicotinamide: the structural landscape in crystal engineering

The idea of a structural landscape is based on the fact that a large number of crystal structures can be associated with a particular organic molecule. Taken together, all these structures constitute the landscape. The landscape includes polymorphs, pseudopolymorphs and solvates. Under certain circumstances, it may also include multicomponent crystals (or co-crystals) that contain the reference molecule as one of the components. Under still other circumstances, the landscape may include the crystal structures of molecules that are closely related to the reference molecule. The idea of a landscape is to facilitate the understanding of the process of crystallization. It includes all minima that can, in principle, be accessed by the molecule in question as it traverses the path from solution to the crystal. Isonicotinamide is a molecule that is known to form many co-crystals. We report here a 2 : 1 co-crystal of this amide with 3,5-dinitrobenzoic acid, wherein an unusual N-H center dot center dot center dot N hydrogen-bonded pattern is observed. This crystal structure offers some hints about the recognition processes between molecules that might be implicated during crystallization. Also included is a review of other recent results that illustrate the concept of the structural landscape.

Guided-wave based structural health monitoring of built-up composite structures using spectral finite element method

The paper discusses basically a wave propagation based method for identifying the damage due to skin-stiffener debonding in a stiffened structure. First, a spectral finite element model (SFEM) is developed for modeling wave propagation in general built-up structures, using the concept of assembling 2D spectral plate elements and the model is then used in modeling wave propagation in a skin-stiffener type structure. The damage force indicator (DFI) technique, which is derived from the dynamic stiffness matrix of the healthy stiffened structure (obtained from the SFEM model) along with the nodal displacements of the debonded stiffened structure (obtained from 2D finite element model), is used to identify the damage due to the presence of debond in a stiffened structure.

Effect of Multiwall Carbon Nanotubes on Electrical and Structural Properties of Polyaniline

Polyaniline (PANI) and PANI/CNT (multiwall carbon nanotubes, CNT) composites were prepared using an oxidative chemical polymerization method with ammonium persulfate and dodecyl benzene sulfonic acid as the oxidizing agent and surfactant, respectively. Fourier-transform infrared spectroscopy spectra illustrate the presence of PANI in the composite and show that some interaction exists between PANI and CNT. Embedding of CNT in the PANI matrix is confirmed by scanning electron micrography. Conductivity of the PANI/CNT composites was higher than that of pure PANI, and the maximum conductivity obtained was 4.44 S/cm at 20 wt.% CNT.

Structural characterization of folded pentapeptides containing centrally positioned beta(R)Val, gamma(R)Val and gamma(S)Val residues

A cylindrical pore of similar to 7.5 angstrom diameter containing a one-dimensional water wire, within the confines of a hydrophobic channel lined with the valine side chain, has been observed in crystals of the peptide Boc-D-Pro-Aib-Val-Aib-Val-OMe (1) (Raghavender et al., 2009, 2010). The synthesis and structural characterization in crystals of three backbone homologated analogues Boc-D-Pro-Aib-beta(3)(R) Val-Aib-Val-OMe (2), Boc-D-Pro-Aib-gamma(4)(R)Val-Aib-Val-OMe (3), Boc-D-Pro-Aib-gamma(4)(S)Val-Aib-Val-OMe (4) are described. Crystal structures of peptides 2, 3 and 4 reveal close-packed arrangements in which no pore was formed. In peptides 2 and 3 the N-terminus D-Pro-Aib segment adopted conformations closely related to Type II' beta-turns, while residues 2-4 form one turn of an alpha beta right-handed C-11 helix in 2 and an alpha gamma C-12 helix in 3. In peptide 4, a continuous left-handed helical structure was observed with the D-Pro-Aib segment forming a Type III' beta-turn, followed by one turn of a left-handed alpha gamma C-12 helix. (C) 2012 Elsevier Ltd. All rights reserved.

Novel Radiation-Induced Properties of Graphene and Related Materials

Interaction of graphene, graphene oxide, and related nanocarbons with radiation gives rise to many novel properties and phenomena. Irradiation of graphene oxide in solid state or in solution by sunlight, UV radiation, or excimer laser radiation reduces it to graphene with negligible oxygen functionalities on the surface. This transformation can be exploited for nanopatterning and for large scale production of reduced graphene oxide (RGO). Laser-induced dehydrogenation of hydrogenated graphene can also be used for this purpose. All such laser-induced transformations are associated with thermal effects. RGO emits blue light on UV excitation, a feature that can be used to generate white light in combination with a yellow emitter. RGO as well as graphene nanoribbons are excellent detectors of infra-red radiation while RGO is a good UV detector.

Thermo-physical and structural studies of sodium zinc borovanadate glasses in the region of high concentration of modifier oxides

This paper reports investigation of Na2O and ZnO modified borovanadate glasses in the highly modified regime of compositions. These glasses have been prepared by microwave route. Ultraviolet (UV) and visible, infrared (IR), Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) and Electron Paramagnetic Resonance (EPR) spectroscopies have been used to characterize the speciation in the glasses. Together with the variation of properties such as molar volume and glass transition temperatures, spectroscopic data indicate that at high levels of modification, ZnO tends to behave like network former. It is proposed that the observed variation of all the properties can be reasonably well understood with a structural model. The model considers that the modification and speciation in glasses are strongly determined by the hierarchy of group electronegativities. Further, it is proposed that the width of the transitions of glasses obtained under same condition reflects the fragility of the glasses. An empirical expression has been suggested to quantify fragility on the basis of width of the transition regions. (C) 2012 Elsevier Ltd. All rights reserved.

beta-Turn Analogues in Model a ss-Hybrid Peptides: Structural Characterization of Peptides Containing ss 2,2Ac6c and ss 3,3Ac6c Residues

The effect of gem-dialkyl substituents on the backbone conformations of beta-amino acid residues in peptides has been investigated by using four model peptides: Boc-Xxx-beta 2,2Ac6c(1-aminomethylcyclohexanecarboxylic acid)-NHMe (Xxx=Leu (1), Phe (2); Boc=tert-butyloxycarbonyl) and Boc-Xxx-beta 3,3Ac6c(1-aminocyclohexaneacetic acid)-NHMe (Xxx=Leu (3), Phe (4)). Tetrasubstituted carbon atoms restrict the ranges of stereochemically allowed conformations about flanking single bonds. The crystal structure of Boc-Leu-beta 2,2Ac6c-NHMe (1) established a C11 hydrogen-bonded turn in the a beta-hybrid sequence. The observed torsion angles (a(similar to-60 degrees, similar to-30 degrees), beta(similar to-90 degrees, similar to 60 degrees, similar to-90 degrees)) corresponded to a C11 helical turn, which was a backbone-expanded analogue of the type III beta turn in aa sequences. The crystal structure of the peptide Boc-Phe-beta 3,3Ac6c-NHMe (4) established a C11 hydrogen-bonded turn with distinctly different backbone torsion angles (a(similar to-60 degrees, similar to 120 degrees), beta(similar to 60 degrees, ?60 degrees, similar to-60 degrees)), which corresponded to a backbone-expanded analogue of the type II beta turn observed in aa sequences. In peptide 4, the two molecules in the asymmetric unit adopted backbone torsion angles of opposite signs. In one of the molecules, the Phe residue adopted an unfavorable backbone conformation, with the energetic penalty being offset by a favorable aromatic interaction between proximal molecules in the crystal. NMR spectroscopy studies provided evidence for the maintenance of folded structures in solution in these a beta-hybrid sequences.