NMR and X-ray crystallographic studies on cyclic tetrapeptide, cyclo (D-Phe-Pro-Sar-Gly)

The conformation of the synthetic cyclic tetrapeptide cyclo(D-Phe-Pro-Sar-Gly) has been determined in solution using the nuclear magnetic resonance technique and in the crystal state by X-ray crystallography. Results showed that the peptide exhibited two different conformations in solution, conformer 1 having cis-trans-cis-trans peptide bonds and conformer 2 having trans-cis-trans-cis peptide bonds. No intramolecular hydrogen bonds were observed in the structures. The X-ray diffraction studies showed the crystals to be orthorhombic with space group P2(1)2(1)2(1) with unit-cell dimensions, a = 5.790, b = 10.344, c = 31.446 A, Z = 4, R = 0.104 for 2301 observed reflections. The crystal structure showed only one type of conformer having cis-trans-cis-trans peptide bonds similar to the conformer 1 in solution.

Study of As2(Se,Te)3 glasses by X-ray absorption and photoelectron spectroscopy

Arsenic selenide-telluride glasses have been investigated by X-ray absorption and photoelectron spectroscopy. The core electron energy shifts and chemical shifts in K-absorption edge measurements associated with the glass-crystal transitions of pure As2Se3 and As2Te3 have been studied. The effect of composition on the core level energy and valence bands of As2(Se,Te)3 glasses, has been discussed. Mixed-composition glasses are found to be considerably ionic.

X-ray photoelectron spectroscopic studies on Se/As2S3 and Sb/As2S3 nanomultilayered film

Photoinduced diffusion in Se/As2S3 and Sb/As2S3 nanomultilayered thin films are studied by X-ray photoelectron spectroscopy (XPS). The XPS measurements show the atomic movements during photoinduced diffusion in Se/As2S3 and Sb/As2S3 nanomultilayered film. The analysis of experimental data describes the nature of light induced changes indifferent structural units. (C) 2009 Elsevier B.V. All rights reserved.

Triplet repeat polymorphism & fragile X syndrome in the Indian context

Mental retardation due to fragile X syndrome is one of the genetic disorders caused by tripler repeat expansion, CGG repeat involved in this disease is known to exhibit polymorphism even among normal individuals. Here we describe the development of suitable probes for detection of polymorphism in CGG repeat at FMR1 locus as well as the diagnosis of fragile X syndrome. Using these methods polymorphism at the FMR1 locus has been examined in 161 individuals. Ninety eight patients with unclassified mental retardation were examined, of whom 7 were found to have the expanded (CGG) allele at the FMR1 locus, The hybridization pattern for two patients has been presented as representative data.

Oxidation of bis-(2-hydroxy-1-naphthyl)methane with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. X-Ray crystal structure of a novel product

A novel compound obtained by the oxidation of the title compound with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone has been assigned structure (5) on the basis of spectral data and X-ray crystal structure analysis.

X-ray spectroscopic studies of amorphous materials

Measurement of the chemical shifts ΔE of the K-absorption edge in both crystalline and amorphous states of several solids shows that ΔE is generally smaller in the amorphous state. More covalent solids appear to be associated with small values of ΔE.

Synthesis, structural and ferromagnetic properties of La1-xKxMnO3 (0.0 <= x <= 0.25) phases by solution combustion method

We describe the solution combustion synthesis and characterization of La1-xKxMnO3 (0.0 <= x <= 0.25) perovskite phases, which is a low temperature initiated, rapid route to prepare metal oxides. As-synthesized compounds are amorphous in nature; crystallinity was observed on heating at 800 degrees C for 5 min. Structural parameters were determined by the Rietveld refinement method using powder XRD data. Parent LaMnO3 compound crystallizes in the orthorhombic structure (space group Pbnm, No. 62). Potassium substituted compounds were crystallized with rhombohedral symmetry (space group R-3c, No. 167). The ratio of the Mn3+/Mn4+ was determined by the iodometric titration. The Fourier transform infrared spectrum (FTIR) shows two absorption bands for Mn-O stretching vibration (v, mode), Mn-O-Mn deformation vibration (v(b) mode) around 600 cm(-1) and 400 cm(-1) for the compositions, x = 0.0, 0.05 and 0-10. Four-probe electrical resistivity measurements reveal a composition controlled metal to insulator transition (TM-1), the maximum TM-1 was observed for the composition La0.85K0.15MnO3 at 287 K. Room temperature vibrating sample magnetometer data indicate that for the composition up to x = 0-10, the compounds are paramagnetic whereas composition with x = 0.15, 0.20 and 0.25 show magnetic moments of 27, 29 and 30 emu/g, respectively.

Structure and phase transition of the (1-x)PbTiO3-(x)BiAlO3 system

The system (1 - x)PbTiO3 - (x)BiAlO3 has been studied with regard to its structure and phase transition behaviour using x-ray, neutron and dielectric measurements. The structure is tetragonal within the solid solubility limit (x < 0.25). Interatomic distance analysis revealed that the Pb-O bond lengths remain unaffected and the only the Ti-O lengths are altered by BiAlO3 substitution. The results are suggestive of a crossover from and A-site & B site driven ferroelectric system for x = 0 to a dominant A-site driven ferroelectric system for higher x. This cross-over is brought about by (i) a reduction in the contribution to the ferroelectric stability from B-site cations due to dilution of the Ti-sublattice by Al and (ii) a reinforcement to the stability of the ferroelectric state by the A-site cations by the Bi+3 cations..

Structure, dynamics, and interactions of jacalin. Insights from molecular dynamics simulations examined in conjunction with results of X-ray studies

Molecular dynamics simulations have been carried out on all the jacalin-carbohydrate complexes of known structure, models of unliganded molecules derived from the complexes and also models of relevant complexes where X-ray structures are not available. Results of the simulations and the available crystal structures involving jacalin permit delineation of the relatively rigid and flexible regions of the molecule and the dynamical variability of the hydrogen bonds involved in stabilizing the structure. Local flexibility appears to be related to solvent accessibility. Hydrogen bonds involving side chains and water bridges involving buried water molecules appear to be important in the stabilization of loop structures. The lectin-carbohydrate interactions observed in crystal structures, the average parameters pertaining to them derived from simulations, energetic contribution of the stacking residue estimated from quantum mechanical calculations, and the scatter of the locations of carbohydrate and carbohydrate-binding residues are consistent with the known thermodynamic parameters of jacalin-carbohydrate interactions. The simulations, along with X-ray results, provide a fuller picture of carbohydrate binding by jacalin than provided by crystallographic analysis alone. The simulations confirm that in the unliganded structures water molecules tend to occupy the positions occupied by carbohydrate oxygens in the lectin-carbohydrate complexes. Population distributions in simulations of the free lectin, the ligands, and the complexes indicate a combination of conformational selection and induced fit. Proteins 2009; 77:760-777.

Nd2O3 : Eu3+ nanocrystalline phosphor - a new potential thermoluminescing material for dosimetry

Nanoparticles of trivalent Eu3+-doped Nd2O3 phosphors have been prepared using a low-temperature solution combustion method with metal nitrate as precursor and oxalyldihydrazide as a fuel at a fairly low temperature (<500 degrees C) and in a very short time (<5 min). A powder X-ray diffraction pattern reveals that cubic Nd2O3 : Eu3+ crystallites are directly obtained without the requirement of further calcinations. The crystallite size, evaluated from Scherer's formula, was found to be in the range of 20-30 nm. The microstructure and morphology were studied by scanning electron microscopy, which showed the phosphor to be foamy and fluffy in nature. Thermoluminescence characteristics of the Nd2O3 : Eu3+ have been studied using gamma irradiation. These demonstrate that the phosphor is suitable for use as a dosimeter.

Contribution from unresolved discrete sources to the extragalactic gamma-ray background (EGRB)

The origin of the extragalactic gamma-ray background (EGRB) is still an open question, even nearly forty years after its discovery. The emission could originate either from truly diffuse processes or from unresolved point sources. Although the majority of the 271 point sources detected by EGRET (Energetic Gamma Ray Experiment Telescope) are unidentified, of the identified sources, blazars are the dominant candidates. Therefore, unresolved blazars may be considered the main contributor to the EGRB, and many studies have been carried out to understand their distribution, evolution and contribution to the EGRB. Considering that gamma-ray emission comes mostly from jets of blazars and that the jet emission decreases rapidly with increasing jet to line-of-sight angle, it is not surprising that EGRET was not able to detect many large inclination angle active galactic nuclei (AGNs). Though Fermi could only detect a few large inclination angle AGNs during the first three months of its survey, it is expected to detect many such sources in the near future. Since non-blazar AGNs are expected to have higher density as compared to blazars, these could also contribute significantly to the EGRB. In this paper, we discuss contributions from unresolved discrete sources including normal galaxies, starburst galaxies, blazars and off-axis AGNs to the EGRB.

Structural Investigation of Activated Lattice Oxygen in Ce1-xSnxO2 and Ce1-x-ySnxPdyO2-delta by EXAFS and DFT calculation

Substitution of Sn4+ ion in CeO2 creates activated oxygen in Ce0.8Sn0.2O2 leading to higher oxygen storage capacity compared to Ce0.8Zr0.2O2. With Pd ion substitution in Ce0.8Sn0.2O2,activation of oxygen is further enhanced as observed from the H-2/TPR study. Both EXAFS analysis and DFT calculation reveal that in the solid solution Ceexhibits 4 + 4 coordination, Sri exhibits 4 + 2 + 2 coordination and Pd has 4 + 3 coordination. While the oxygen in the First four coordination with short M-O bonds are strongly held in the lattice, the oxygens in the second and higher coordinations with long M-O bonds are weakly bound, and they are the activated oxygen ill the lattice. Bond valence analysis shows that oxygen with valencies as low its 1.65 are created by the Sn and Pd ion Substitution. Another interesting observation is that H-2/TPR experiment of Ce1-xSnxO2 shows a broad peak starting from 200 to 500 degrees C, while the same reduction is achieved in a single step at similar to 110 degrees C in presence Pd2+ on. Substitution of Pd2+ ion thus facilitates synergistic reduction of the catalyst at lower temperature. We have shown that simultaneous reduction of the Ce4+ and Sr4+ ions by Pd-0 is the synergistic interaction leading to high oxygen storage capacity at low temperature.

Search for chaos in neutron star systems: Is Cyg X-3 a black hole?

The accretion disk around a compact object is a nonlinear general relativistic system involving magnetohydrodynamics. Naturally, the question arises whether such a system is chaotic (deterministic) or stochastic (random) which might be related to the associated transport properties whose origin is still not confirmed. Earlier, the black hole system GRS 1915+105 was shown to be low-dimensional chaos in certain temporal classes. However, so far such nonlinear phenomena have not been studied fairly well for neutron stars which are unique for their magnetosphere and kHz quasi-periodic oscillation (QPO). On the other hand, it was argued that the QPO is a result of nonlinear magnetohydrodynamic effects in accretion disks. If a neutron star exhibits chaotic signature, then what is the chaotic/correlation dimension? We analyze RXTE/PCA data of neutron stars Sco X-1 and Cyg X-2, along with the black hole Cyg X-1 and the unknown source Cyg X-3, and show that while Sco X-1 and Cyg X-2 are low dimensional chaotic systems, Cyg X-1 and Cyg X-3 are stochastic sources. Based on our analysis, we argue that Cyg X-3 may be a black hole.

Transition from radiatively inefficient to cooling dominated phase in two temperature accretion disks around black holes

We investigate the transition of a radiatively inefficient phase of a viscous two temperature accreting flow to a cooling dominated phase and vice versa around black holes. Based on a global sub-Keplerian accretion disk model in steady state, including explicit cooling processes self-consistently, we show that general advective accretion flow passes through various phases during its infall towards a black hole. Bremsstrahlung, synchrotron and inverse Comptonization of soft photons are considered as possible cooling mechanisms. Hence the flow governs a much lower electron temperature similar to 10(8) - 10(9.5) K compared to the hot protons of temperature similar to 10(10.2) - 10(11.8) K in the range of the accretion rate in Eddington units 0.01 less than or simiar to (M) over dot less than or similar to 100. Therefore, the solutions may potentially explain the hard X-rays and the gamma-rays emitted from AGNs and X-ray binaries. We finally compare the solutions for two different regimes of viscosity and conclude that a weakly viscous flow is expected to be cooling dominated compared to its highly viscous counterpart which is radiatively inefficient. The flow is successfully able to reproduce the observed minosities of the under-fed AGNs and quasars (e.g. Sgr A*), ultra-luminous X-ray sources (e.g. SS433), as well as the highly luminous AGNs and ultra-luminous quasars (e.g. PKS 0743-67) at different combinations of the mass accretion rate and ratio of specific heats.

Two temperature viscous accretion flows around rotating black holes: Description of under-fed systems to ultra-luminous X-ray sources

We discuss two temperature accretion disk flows around rotating black holes. As we know that to explain observed hard X-rays the choice of Keplerian angular momentum profile is not unique, we consider the sub-Keplerian regime of the disk. Without any strict knowledge of the magnetic field structure, we assume the cooling mechanism is dominated by bremsstrahlung process. We show that in a range of Shakura-Sunyaev viscosity parameter 0.2 greater than or similar to alpha greater than or similar to 0.0005, flow behavior varies widely, particularly by means of the size of disk, efficiency of cooling and corresponding temperatures of ions and electrons. We also show that the disk around a rotating black hole is hotter compared to that around a Schwarzschild black hole, rendering a larger difference between ion and electron temperatures in the former case. With all the theoretical solutions in hand, finally we reproduce the observed luminosities (L) of two extreme cases-the under-fed AGNs and quasars (e.g. Sgr A') with L greater than or similar to 10(33) erg/s to ultra-luminous X-ray sources with L similar to 10(41) erg/s, at different combinations of mass accretion rate, ratio of specific heats, Shakura-Sunyaev viscosity parameter and Kerr parameter, and conclude that Sgr A' may be an intermediate spinning black hole.