X-ray studies on crystalline complexes involving amino acids and peptides. Part XIV: Closed conformation and head-to-tail arrangement in a new crystal form of L-histidine L-aspartate monohydrate

A new form of L-histidine L-aspartate monohydrate crystallizes in space group P22 witha = 5.131(1),b = 6.881(1),c= 18.277(2) Å,β= 97.26(1)° and Z = 2. The structure has been solved by the direct methods and refined to anR value of 0.044 for 1377 observed reflections. Both the amino acid molecules in the complex assume the energetically least favourable allowed conformation with the side chains staggered between the α-amino and α-scarboxylate groups. This results in characteristic distortions in some bond angles. The unlike molecules aggregate into alternating double layers with water molecules sandwiched between the two layers in the aspartate double layer. The molecules in each layer are arranged in a head-to-tail fashion. The aggregation pattern in the complex is fundamentally similar to that in other binary complexes involving commonly occurring L amino acids, although the molecules aggregate into single layers in them. The distribution of crystallographic (and local) symmetry elements in the old form of the complex is very different from that in the new form. So is the conformation of half the histidine molecules. Yet, the basic features of molecular aggregation, particularly the nature and the orientation of head-to-tail sequences, remain the same in both the forms. This supports the thesis that the characteristic aggregation patterns observed in crystal structures represent an intrinsic property of amino acid aggregation.

Neutral Nanosheets that Gel: Exfoliated Layered Double Hydroxides in Toluene

A simple strategy to exfoliate inorganic layered double hydroxide (LDH) solids to their ultimate constituent, intact single layers of nanometer thickness and micrometer size, is presented. The procedure involves intercalation of an ionic surfactant that forms a hydrophobic anchored surfactant bilayer in the galleries of the solid followed by simply stirring the intercalated solid in toluene. The method is rapid but at the same time gentle enough to produce exfoliated nanosheets of regular morphology that are electrically neutral and form stable gels at higher concentrations. In this Letter, we describe the phenomena and use molecular dynamics simulations to show that exfoliation of the LDH in toluene is a consequence of the modification of the cohesive dispersive interactions between surfactant chains anchored on opposing inorganic sheets by the toluene molecules. The toluene molecules function as a molecular glue, holding the surfactant-anchored LDH sheets together, leading to gel formation.

Pulsed laser deposited ZnO/ZnO:Li multilayer for blue light emitting diodes

Thin films of ZnO, Li doped ZnO (ZLO) and multilayer of ZnO and ZLO (ZnO/ZLO) were grown on silicon and corning glass substrates by pulsed laser deposition technique. Single phase formation and the crystalline qualities of the films were analyzed by X-ray diffraction and Li composition in the film was investigated to be 15 wt% by X-ray photoelectron spectroscopy. Raman spectrum reveals the hexagonal wurtzite structure of ZnO, ZLO and ZnO/ZLO multilayer and confirms the single phase formation. Films grown on corning glass shows more than 80% transmittance in the visible region and the optical band gaps were calculated to be 3.245, 3.26 and 3.22 eV for ZnO, ZLO and ZnO/ZLO, respectively. An efficient blue emission was observed in all films which were grown on silicon (1 0 0) substrate by photoluminescence (PL). PL measurements at different temperatures reveal that the PL emission intensity of ZnO/ZLO multilayer was weakly dependent on temperature as compared to the single layers of ZnO and ZLO and the wavelength of emission was independent of temperature. Our results indicate that ZnO/ZLO multilayer can be used for the fabrication of blue light emitting diodes. (C) 2011 Elsevier B.V. All rights reserved.

Engineering New Layered Solids from Exfoliated Inorganics: a Periodically Alternating Hydrotalcite - Montmorillonite Layered Hybrid

Two-dimensional (2D) nanosheets obtained by exfoliating inorganic layered crystals have emerged as a new class of materials with unique attributes. One of the critical challenges is to develop robust and versatile methods for creating new nanostructures from these 2D-nanosheets. Here we report the delamination of layered materials that belonging to two different classes - the cationic clay, montmorillonite, and the anionic clay, hydrotalcite - by intercalation of appropriate ionic surfactants followed by dispersion in a non-polar solvent. The solids are delaminated to single layers of atomic thickness with the ionic surfactants remaining tethered to the inorganic and consequently the nanosheets are electrically neutral. We then show that when dispersions of the two solids are mixed the exfoliated sheets self-assemble as a new layered solid with periodically alternating hydrotalcite and montmorillonite layers. The procedure outlined here is easily extended to other layered solids for creating new superstructures from 2D-nanosheets by self-assembly.

Vortex dynamics at rf frequencies in Bi2Sr2CaCu2O8 single crystals

We have studied the low magnetic field high temperature region of the H-T phase diagram of Bi2Sr2CaCu2O8 single crystals using the technique of non-resonant rf response at a frequency of 20 MHz. With H(rf)parallel to a, H parallel to c, the isothermal magnetic field scans below T-c show that the frequency f(H) of the tank circuit decreases continuously with increase in H before saturating at H similar to H-D(T). Such a decrease in f(H) reflects increasing rf penetration into the weakly screened region between CuO bilayers. The saturation of f(H) at its lowest value for H similar to H-D(T) indicates complete rf penetration land hence the disappearance of field dependence) due to the vanishing of the screening rf currents I-rf(c) in those regions or equivalently when the phase coherence between adjacent superconducting layers vanishes. Therefore H,(T) represents the decoupling of the adjacent superconducting bilayers, and hence also a 3D to 2D decoupling transition of the vortex structure. Simultaneous monitoring of the field dependent rf power dissipation P(H) shows a maximum in dP/dH at H-D(T). The observed H-D(T) line in many crystals is in excellent agreement with the (l/t-1) behavior proposed for decoupling.

Amino Acid Based MOFs: Synthesis, Structure, Single Crystal to Single Crystal Transformation, Magnetic and Related Studies in a Family of Cobalt and Nickel Aminoisophthales

Four new 5-aminoisophthalates of cobalt and nickel have been prepared employing hydro/solvothermal methods: [Co2(C8H5NO4)2(C4H4N2)(H2O)2]·3H2O (I), [Ni2(C8H5NO4)2(C4H4N2)(H2O)2]·3H2O (II), [Co2(H2O)(μ3-OH)2(C8H5NO4)] (III), and [Ni2(H2O)(μ3-OH)2(C8H5NO4)] (IV). Compounds I and II are isostructural, having anion-deficient CdCl2 related layers bridged by a pyrazine ligand, giving rise to a bilayer arrangement. Compounds III and IV have one-dimensional M−O(H)−M chains connected by the 5-aminoisophthalate units forming a three-dimensional structure. The coordinated as well as the lattice water molecules of I and II could be removed and inserted by simple heating−cooling cycles under the atmospheric conditions. The removal of the coordinated water molecule is accompanied by changes in the coordination environment around the M2+ (M = Co, Ni) and color of the samples (purple to blue, Co; green to dark yellow, Ni). This change has been examined by a variety of techniques that include in situ single crystal to single crystal transformation studies and in situ IR and UV−vis spectroscopic studies. Magnetic studies indicate antiferromagnetic behavior in I and II, a field-induced magnetism in III, and a canted antiferromagnetic behavior in IV.

Defect characterization of KTP single crystals

Potassium titanyl phosphate (KTP) is a relatively new nonlinear optical material with excellent combination of physical properties. This paper presents the combined etching and X-ray topographic studies carried out on KTP crystals with a view to characterizing their defects. KTP crystals employed in this investigation were grown from flux. Optical microscopic study of habit faces revealed growth layers and growth hillocks on (100) and (011) faces respectively. Etching of (011) habit faces proved that growth hillocks corresponded to the emergence point of dislocation out crops on these faces. The suitability of the new etchant to reveal dislocation was confirmed by etching the matched pairs obtained by cleaving. The defects present in the crystal were also studied by X-ray topography. The defect configuration in these crystals is characteristic of crystals grown from solution. The dislocations arc predominantly linear with their origin either at the nucleation centre or inclusions. In general, grown crystals were found to have low dislocation density and often large volumes of crystals free from dislocation could be obtained.

Probing Single and Bilayer Graphene Field Effect Transistors By Raman Spectroscopy

This article is a review of our work related to Raman studies of single layer and bilayer graphenes as a function Fermi level shift achieved by electrochemically top gating a field effect transistor. Combining the transport and in situ Raman studies of the field effect devices, a quantitative understanding is obtained of the phonon renormalization due to doping of graphene. Results are discussed in the light of time dependent perturbation theory, with electron phonon coupling parameter as an input from the density functional theory. It is seen that phonons near and Gamma and K points of the Brillouin zone are renormalized very differently by doping. Further, Gamma-phonon renormalization is different in bilayer graphene as compared to single layer, originating from their different electronic band structures near the zone boundary K-point. Thus Raman spectroscopy is not only a powerful probe to characterize the number of layers and their quality in a graphene sample, but also to quantitatively evaluate electron phonon coupling required to understand the performance of graphene devices.

Effect of thermal annealing on the dielectric properties of KTiOPO4 single crystals

Dielectric properties of potassium titanyl phosphate have been investigated as a function of thickness and frequency, as well as annealing treatment under various atmospheres. The low frequency dielectric constant of KTP crystals is shown to depend upon the sample thickness, and this feature is attributed to the existence of surface layers. The frequency-dependent dielectric response of KTP exhibits a non-Debye type relaxation, with a distribution of relaxation times. The dielectric behavior of KTP samples annealed in various atmospheres shows that the low frequency dielectric constant is influenced by the contribution from the space charge layers. Prolonged annealing of the samples leads to a surface degradation, resulting in the formation of a surface layer of lower dielectric constant. This surface degradation is least when annealed in the presence of dry oxygen. From the analysis of the dielectric data using complex electric modulus, alpha(m) has been evaluated for the virgin and annealed samples. (C) 1996 American Institute of Physics.

Synthesis of single-walled carbon nanotubes using binary (Fe, Co, Ni) alloy nanoparticles prepared in situ by the reduction of oxide solid solutions

Passing a H-2-CH4 mixture over oxide spinels containing two transition elements as in Mg0.8MyMz'Al2O4 (M, M' = Fe, Co or Ni, y + z = 0.2) at 1070 degrees C produces small alloy nanoparticles which enable the formation of carbon nanotubes. Surface area measurements are found to be useful for assessing the yield and quality of the nanotubes. Good-quality single-walled nanotubes (SWNTs) have been obtained in high yields with the FeCo alloy nanoparticles, as evidenced by transmission electron microscope images and surface area measurements. The diameter of the SWNTs is in the 0.8-5 nm range, and the multiwalled nanotubes, found occasionally, possess very few graphite layers. (C) 1999 Elsevier Science B.V. All rights reserved.

Suppressed rf dissipation in 107Ag17+ ion irradiated Bi2Sr2CaCu2O8 single crystals by enhanced flux line tilt modulus

We have studied the isothermal, magnetic field (H‖c) dependent rf power P(H) dissipation (Hrf‖a) in the superconducting state of Bi2Sr2CaCu2O8 single crystals prior to and after irradiation with 250 MeV 107Ag17+ ions. In the pristine state, P(H) shows an initial decrease with increase in field, reaches a minimum at HM(T) and increases monotonically for H>HM(T). This behavior arises when the electromagnetic coupling between the pancake vortices in adjacent CuO layers becomes dominant on increasing the field and minimizes the distortions of the flux lines by confining the 2D vortices. In the post irradiated state, such an initial decrease and the minimum in P(H) is not observed but only a much reduced rf dissipation that monotonically increases with field from H = 0 onwards is seen. We attribute this difference to the strong enhancement of the tilt modulus C44 of the flux lines on irradiation when the pancake vortices in adjacent CuO bilayers are pinned along the track forming a well-stacked flux line in the field direction (‖c). We have also observed that the rf dissipation disappears at a certain temperature Tsf, at which the normal core of the flux line becomes commensurate with the columnar track diameter.

State Dependent Attempt Rate modeling of single cell IEEE 802.11 WLANs with homogeneous nodes and Poisson packet arrivals

We study a State Dependent Attempt Rate (SDAR) approximation to model M queues (one queue per node) served by the Carrier Sense Multiple Access with Collision Avoidance (CSMA/CA) protocol as standardized in the IEEE 802.11 Distributed Coordination Function (DCF). The approximation is that, when n of the M queues are non-empty, the (transmission) attempt probability of each of the n non-empty nodes is given by the long-term (transmission) attempt probability of n saturated nodes. With the arrival of packets into the M queues according to independent Poisson processes, the SDAR approximation reduces a single cell with non-saturated nodes to a Markovian coupled queueing system. We provide a sufficient condition under which the joint queue length Markov chain is positive recurrent. For the symmetric case of equal arrival rates and finite and equal buffers, we develop an iterative method which leads to accurate predictions for important performance measures such as collision probability, throughput and mean packet delay. We replace the MAC layer with the SDAR model of contention by modifying the NS-2 source code pertaining to the MAC layer, keeping all other layers unchanged. By this model-based simulation technique at the MAC layer, we achieve speed-ups (w.r.t. MAC layer operations) up to 5.4. Through extensive model-based simulations and numerical results, we show that the SDAR model is an accurate model for the DCF MAC protocol in single cells. (C) 2012 Elsevier B.V. All rights reserved.

Analysis of composite single lap joints using numerical and experimental approach

Adhesives are widely used to execute the assembly of aerospace and automotive structures due to their ability to join dissimilar materials, reduced stress concentration, and improved fatigue resistance. The mechanical behavior of adhesive joints can be studied either using analytical models or by conducting mechanical tests. However, the complexity owing to multiple interfaces, layers with different properties, material and geometric nonlinearity and its three-dimensional nature combine to increase the difficulty in obtaining an overall system of governing equations to predict the joint behavior. On the other hand, experiments are often time consuming and expensive due to a number of parameters involved. Finite element analysis (FEA) is profoundly used in recent years to overcome these limitations. The work presented in this paper involves the finite element modeling and analysis of a composite single lap joint where the adhesive-adherend interface region was modeled using connector elements. The computed stresses were compared with the experimental stresses obtained using digital image correlation technique. The results showed an agreement. Further, the failure load predicted using FEA was found to be closer to the actual failure load obtained by mechanical tests.

Prussian blue as a single precursor for synthesis of Fe/Fe3C encapsulated N-doped graphitic nanostructures as bi-functional catalysts

We report a unique, single source precursor Prussian blue (iron(III) ferrocyanide (Fe-4(III)Fe-II(CN)(6)](3))) for the synthesis of Fe/Fe3C nanoparticle encapsulated N-doped graphitic layers and bamboo-like graphitic nanotubes. Hollow N-doped graphite (N-HG) nanostructures are obtained when the encapsulated nanostructures are treated with an acid. Both the encapsulated nanostructures and N-HG are shown to be applicable as bi-functional electrocatalysts for oxygen reduction (ORR) and oxygen evolution reactions (OER). The ORR activity is shown to be improved for N-HG and is comparable to commercial Pt/C. On the other hand, encapsulated nanostructures exhibit OER activity with long-term stability comparable to commercial RuO2.

Prussian blue as a single precursor for synthesis of Fe/Fe3C encapsulated N-doped graphitic nanostructures as bi-functional catalysts

We report a unique, single source precursor Prussian blue (iron(III) ferrocyanide (Fe-4(III)Fe-II(CN)(6)](3))) for the synthesis of Fe/Fe3C nanoparticle encapsulated N-doped graphitic layers and bamboo-like graphitic nanotubes. Hollow N-doped graphite (N-HG) nanostructures are obtained when the encapsulated nanostructures are treated with an acid. Both the encapsulated nanostructures and N-HG are shown to be applicable as bi-functional electrocatalysts for oxygen reduction (ORR) and oxygen evolution reactions (OER). The ORR activity is shown to be improved for N-HG and is comparable to commercial Pt/C. On the other hand, encapsulated nanostructures exhibit OER activity with long-term stability comparable to commercial RuO2.