X-ray photoelectron spectroscopy: a unique tool to determine the internal heterostructure of nanoparticles

We review the existing literature on the application of X-ray photoelectron spectroscopy in the study of nanocrystals. The unique ability of this technique to provide quantitative and reliable descriptions of highly complex internal structures of a variety of nanocrystals has been discussed in detail. We show that an accurate description of the nanocrystal internal structure is crucial and a prerequisite to understand many different properties, particularly optical properties, of such nanocrystal systems. We also discuss limitations and future outlook of this technique.

Crossover from photodarkening to photobleaching in a-GexSe100-x thin films

In this Letter, we present the interesting results of photodarkening (PD), transition toward photostability, and a slow crossover from PD to photobleaching when composition of the chalcogenide glassy thin film changes from Ge-deficient to rich. A subsequent Raman analysis on these as-prepared and irradiated samples provide the direct evidence of photoinduced structural rearrangement, i.e., photocrystallization of Se and the removal of edge-sharing GeSe4 tetrahedra. Further, our experimental results clearly demonstrate that light-induced effects can be effectively controlled by choosing the right composition and provide valuable information on synthesizing photostable/sensitive glasses.

Affinity of a galactose-specific legume lectin from Dolichos lablab to adenine revealed by X-ray cystallography

Crystal structure analysis of a galactose-specific lectin from a leguminous food crop Dolichos lablab (Indian lablab beans) has been carried out to obtain insights into its quaternary association and lectin-carbohydrate interactions. The analysis led to the identification of adenine binding sites at the dimeric interfaces of the heterotetrameric lectin. Structural details of similar adenine binding were reported in only one legume lectin, Dolichos biflorus, before this study. Here, we present the structure of the galactose-binding D. lablab lectin at different pH values in the native form and in complex with galactose and adenine. This first structure report on this lectin also provides a high resolution atomic view of legume lectin-adenine interactions. The tetramer has two canonical and two DB58-like interfaces. The binding of adenine, a non-carbohydrate ligand, is found to occur at four hydrophobic sites at the core of the tetramer at the DB58-like dimeric interfaces and does not interfere with the carbohydrate-binding site. To support the crystallographic observations, the adenine binding was further quantified by carrying out isothermal calorimetric titration. By this method, we not only estimated the affinity of the lectin to adenine but also showed that adenine binds with negative cooperativity in solution.

Crystallization and preliminary X-ray diffraction studies of Staphylococcus aureus homoserine dehydrogenase

Staphylococcus aureus is a Gram-positive nosocomial pathogen. The prevalence of multidrug-resistant S. aureus strains in both hospital and community settings makes it imperative to characterize new drug targets to combat S. aureus infections. In this context, enzymes involved in cell-wall maintenance and essential amino-acid biosynthesis are significant drug targets. Homoserine dehydrogenase (HSD) is an oxidoreductase that is involved in the reversible conversion of l-aspartate semialdehyde to l-homoserine in a dinucleotide cofactor-dependent reduction reaction. HSD is thus a crucial intermediate enzyme linked to the biosynthesis of several essential amino acids such as lysine, methionine, isoleucine and threonine.

Cloning, expression, purification, crystallization and preliminary X-ray studies of argininosuccinate lyase (Rv1659) from Mycobacterium tuberculosis

The last enzyme in the arginine-biosynthesis pathway, argininosuccinate lyase, from Mycobacterium tuberculosis has been cloned, expressed, purified and crystallized, and preliminary X-ray studies have been carried out on the crystals. The His-tagged tetrameric enzyme with a subunit molecular weight of 50.9 kDa crystallized with two tetramers in the asymmetric unit of the orthorhombic unit cell, space group P2(1)2(1)2(1). Molecular-replacement calculations and self-rotation calculations confirmed the space group and the tetrameric nature of the molecule.

X-ray diffraction and Mossbauer spectroscopy studies of cementite dissolution in cold-drawn pearlitic steel

Cementite dissolution in cold-drawn pearlitic steel (0.8 wt.% carbon) wires has been studied by quantitative X-ray diffraction (XRD) and Mossbauer spectroscopy up to drawing strain 1.4. Quantification of cementite-phase fraction by Rietveld analysis has confirmed more than 50% dissolution of cementite phase at drawing strain 1.4. It is found that the lattice parameter of the ferrite phase determined by Rietveld refinement procedure remains nearly unchanged even after cementite dissolution. This confirms that the carbon atoms released after cementite dissolution do not dissolve in the ferrite lattice as Fe-C interstitial solid solution. Detailed analysis of broadening of XRD line profiles for the ferrite phase shows high density of dislocations (approximate to 10(15)/m(2)) in the ferrite matrix at drawing strain 1.4. The results suggest a dominant role of 111 screw dislocations in the cementite dissolution process. Post-deformation heat treatment leads to partial annihilation of dislocations and restoration of cementite phase. Based on these experimental observations, further supplemented by TEM studies, we have suggested an alternative thermodynamic mechanism of the dissolution process.

ENDOR studies of hydrogen bonding of the AsO44- centre in x-ray irradiated KH2AsO4

We here report what we believe to be an important method for studying hydrogen bonding in systems containing a paramagnetic centre. The technique of electron-nuclear double resonance ( ENDOR) has been applied to study the hydrogen-bond network around the AsO44-. centre in X-ray irradiated KH2AsO4. ENDOR transitions from several sets of hydrogen nuclei surrounding the centre were observed at 4.2 degrees K and the spectra for two sets of neighbouring nuclei are identified. The angular dependences for these spectra are fitted with a spin-Hamiltonian to obtain the isotropic and anisotropic magnetic hyperfine constants. The results are discussed in terms of the available spectroscopic and crystallographic data on KH2AsO4 and the order-disorder model of ferroelectrictricity in this class of crystals.

Revisiting SW J2000.6+3210: a persistent Be X-ray pulsar?

We present a detailed timing and spectral analysis of the Be X-ray binary SW J2000.6+3210 discovered by the Burst Alert Telescope Galactic plane survey. Two Suzaku observations of the source made at six months interval, reveal pulsations at similar to 890 s for both observations with a much weaker pulse fraction in the second one. Pulsations are clearly seen in the energy band of 0.3-10 keV of X-ray Imaging Spectrometer for both observations and at high energies up to 40 keV for the second observation. The broad-band X-ray spectrum is consistent with a power-law and high-energy cut-off model along with a hot blackbody component. No change in spectral parameters is detected between the observations. We have also analysed several short observations of the source with Swift/XRT and detected only a few per cent variation in flux around a mean value of 3.5 x 10(-11) erg cm(-2) s(-1). The results indicate that SW J2000.6+3210 is a member of persistent Be X-ray binaries which have the same broad characteristics as this source.

Valence band electronic structure of Nd1-xYxMnO3 using X-ray absorption, photoemission and GGA plus U calculations

The electronic structures of Nd1-xYxMnO3 (x=0-0.5) were studied using X-ray absorption near-edge structure (XANES) at the Mn L-3,L-2- and O K-edge along with valence-band photoemission spectroscopy (VB-PES). The systematic increase in white-line intensity of the Mn L-3,L-2-edge with doping, suggests a decrease in the occupancy of Mn 3d orbitals. The O K-edge XANES shows a depletion of unoccupied states above the Fermi energy. The changes in the O K-edge spectra due to doping reflects an increase in the Jahn-Teller distortion. The VB-PES shows broadening of the features associated with Mn 3d and O 2p hybridized states and the shift of these features to a slightly higher binding energy in agreement with our GGA + U calculations. The system shows a net shift of the occupied and unoccupied states away from the Fermi energy with doping. The shift in theoretical site-projected density of states of x=0.5 composition with respect to x=0 suggest a subtle change from a charge transfer to Mott-Hubbard type insulator. (C) 2013 Elsevier B.V. All rights reserved.

Electrical switching behavior of amorphous Ge15Te85 Si--x(x) thin films with phase change memory applications

Amorphous Ge15Te85-xSix thin film switching devices (1 <= x <= 6) have been deposited in sandwich geometry, on glass substrates with aluminum electrodes, by flash evaporation technique. These devices exhibit memory type electrical switching, like bulk Ge15Te85-xSix glasses. However, unlike the bulk glasses, a-Ge15Te85-xSix films exhibit a smooth electrical switching behavior. The electrical switching fields of a-Ge15Te85-xSix thin film samples are also comparable with other chalcogenide samples used in memory applications. The switching fields of a-Ge15Te85-xSix films have been found to increase with increasing Si concentration. Also, the optical band gap of a-Ge15Te85-xSix films is found to increase with Si content. The observed results have been understood on the basis of increase in network connectivity and rigidity with Si addition. (C) 2013 Elsevier Ltd. All rights reserved.

Ligational behaviour of (E)-2-amino-N ` -1-(2-hydroxyphenyl) ethylidene]benzohydrazide towards later 3d metal ions: X-ray crystal structure of nickel(IV) complex

Ligational behaviour of (E)-2-amino-N'-1-(2-hydroxyphenyl)ethylidene]benzohydrazide (Aheb) towards later 3d metal ionscopper(II), cobalt(II), manganese(II), zinc(II), cadmium(II) and nickel(IV)] has been studied. Their structures have been elucidated on the basis of spectral (IR, H-1 NMR, UV-Vis, EPR and FAB-mass), elemental analyses, conductance measurements, magnetic moments, and thermal studies. During complexation Ni(II) ion has got oxidized to Ni(IV). The changes in the bond parameters of the ligand on complexation has been discussed by comparing the crystal structure of the ligand with that of its Ni(IV) complex. The X-ray single crystal analysis of Ni(aheb)(2)]Cl-2 center dot 4H(2)O has confirmed an octahedral geometry around the metal ion. EPR spectra of the Cu(II) complex in polycrystalline state at room (300 K) and liquid nitrogen temperature (77 K) were recorded and their salient features are reported. (C) 2014 Elsevier B.V. All rights reserved.

Local disorder investigation in NiS2-xSex using Raman and Ni K-edge x-ray absorption spectroscopies

We report on Raman and Ni K-edge x-ray absorption investigations of a NiS2-xSex (with x = 0.00, 0.50/0.55, 0.60, and 1.20) pyrite family. The Ni K-edge absorption edge shows a systematic shift going from an insulating phase (x = 0.00 and 0.50) to a metallic phase (x = 0.60 and 1.20). The near-edge absorption features show a clear evolution with Se doping. The extended x-ray absorption fine structure data reveal the evolution of the local structure with Se doping which mainly governs the local disorder. We also describe the decomposition of the NiS2-xSex Raman spectra and investigate the weights of various phonon modes using Gaussian and Lorentzian profiles. The effectiveness of the fitting models in describing the data is evaluated by means of Bayes factor estimation. The Raman analysis clearly demonstrates the disorder effects due to Se alloying in describing the phonon spectra of NiS2-xSex pyrites.

The Relationship Between Solar Coronal X-Ray Brightness and Active Region Magnetic Fields: A Study Using High-Resolution Hinode Observations

By using high-resolution observations of nearly co-temporal and co-spatial Solar Optical Telescope spectropolarimeter and X-Ray Telescope coronal X-ray data onboard Hinode, we revisit the problematic relationship between global magnetic quantities and coronal X-ray brightness. Co-aligned vector magnetogram and X-ray data were used for this study. The total X-ray brightness over active regions is well correlated with integrated magnetic quantities such as the total unsigned magnetic flux, the total unsigned vertical current, and the area-integrated square of the vertical and horizontal magnetic fields. On accounting for the inter-dependence of the magnetic quantities, we inferred that the total magnetic flux is the primary determinant of the observed integrated X-ray brightness. Our observations indicate that a stronger coronal X-ray flux is not related to a higher non-potentiality of active-region magnetic fields. The data even suggest a slightly negative correlation between X-ray brightness and a proxy of active-region non-potentiality. Although there are small numerical differences in the established correlations, the main conclusions are qualitatively consistent over two different X-ray filters, the Al-poly and Ti-poly filters, which confirms the strength of our conclusions and validate and extend earlier studies that used low-resolution data. We discuss the implications of our results and the constraints they set on theories of solar coronal heating.

Synthesis, X-ray structure and in vitro cytotoxicity studies of Cu(I/II) complexes of thiosemicarbazone: special emphasis on their interactions with DNA

4-(p-X-phenyl)thiosemicarbazone of napthaldehyde {where X = Cl (HL1) and X = Br (HL2)}, thiosemicarbazone of quinoline-2-carbaldehyde (HL3) and 4-(p-fluorophenyl) thiosemicarbazone of salicylaldehyde (H2L4) and their copper(I) {Cu(HL1)(PPh3)(2)Br]center dot CH3CN (1) and Cu(HL2)(PPh3)(2)Cl]center dot DMSO (2)} and copper(II) {((Cu2L2Cl)-Cl-3)(2)(mu-Cl)(2)]center dot 2H(2)O (3) and Cu(L-4)(Py)] (4)} complexes are reported herein. The synthesized ligands and their copper complexes were successfully characterized by elemental analysis, cyclic voltammetry, NMR, ESI-MS, IR and UV-Vis spectroscopy. Molecular structures of all the Cu(I) and Cu(II) complexes have been determined by X-ray crystallography. All the complexes (1-4) were tested for their ability to exhibit DNA-binding and - cleavage activity. The complexes effectively interact with CT-DNA possibly by groove binding mode, with binding constants ranging from 10(4) to 10(5) M-1. Among the complexes, 3 shows the highest chemical (60%) as well as photo-induced (80%) DNA cleavage activity against pUC19 DNA. Finally, the in vitro antiproliferative activity of all the complexes was assayed against the HeLa cell line. Some of the complexes have proved to be as active as the clinical referred drugs, and the greater potency of 3 may be correlated with its aqueous solubility and the presence of the quinonoidal group in the thiosemicarbazone ligand coordinated to the metal.

Determination of band offsets at the Al:ZnO/Cu2SnS3 interface using X-ray photoelectron spectroscopy

The Al:ZnO/Cu2SnS3 semiconductor heterojunction was fabricated. The structural and optical properties of the semiconductor materials were studied. The band offset at the Al:ZnO/Cu2SnS3 heterojunction was studied using X-ray photoelectron spectroscopy technique. From the measurement of the core level energies and valence band maximum of the constituent elements, the valence band offset was calculated to be -1.1 +/- 0.24 eV and the conduction band offset was 0.9 +/- 0.34 eV. The band alignment at the heterojunction was found to be of type-I. The study of Al:ZnO/Cu2SnS3 heterojunction is useful for solar cell applications. (C) 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.