In situ Raman and synchrotron X-ray diffraction study on crystallization of Choline chloride/Urea deep eutectic solvent under high pressure

NASA Astrophysics Data System (ADS)

Yuan, Chaosheng; Chu, Kunkun; Li, Haining; Su, Lei; Yang, Kun; Wang, Yongqiang; Li, Xiaodong

2016-09-01

Pressure-induced crystallization of Choline chloride/Urea (ChCl/Urea) deep eutectic solvent (DES) has been investigated by in-situ Raman spectroscopy and synchrotron X-ray diffraction. The results indicated that high pressure crystals appeared at around 2.6 GPa, and the crystalline structure was different from that formed at ambient pressure. Upon increasing the pressure, the Nsbnd H stretching modes of Urea underwent dramatic change after liquid-solid transition. It appears that high pressures may enhance the hydrogen bonds formed between ChCl and Urea. P versus T phase diagram of ChCl/Urea DES was constructed, and the crystallization mechanism of ChCl/Urea DES was discussed in view of hydrogen bonds.

Low temperature InP /Si wafer bonding using boride treated surface

NASA Astrophysics Data System (ADS)

Huang, Hui; Ren, Xiaomin; Wang, Wenjuan; Song, Hailan; Wang, Qi; Cai, Shiwei; Huang, Yongqing

2007-04-01

An approach for InP /Si wafer bonding based on boride-solution treatment was presented. The bonding energy is higher than the InP fracture energy by annealing at 280°C. An In0.53Ga0.47As/InP multiple-quantum-well (MQW) structure grown on InP was transferred onto Si substrate via the bonding process. X-ray diffraction and photoluminescence reveal that crystal quality of the bonded MQW was preserved. A thin B2O3-POx-SiO2 oxide layer of about 28nm thick at the bonding interface was detected. X-ray photoelectron spectroscopy and Raman analyses indicate that the formation of oxygen bridging bonds by boride treatment is responsible for the strong fusion obtained at such low temperature.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sathyalakshmi, R.; Bhagavannarayana, G.; Ramasamy, P.

L-(+)-Glutamic acid hydro bromide, an isomorphic salt of L-glutamic acid hydrochloride, was synthesized and the synthesis was confirmed using Fourier transform infrared analysis. Solubility of the material in water was determined. L-Glutamic acid hydro bromide crystals were grown by low temperature solution growth using the solvent evaporation technique. Single crystal X-ray diffraction studies were carried out and the cell parameters, atomic co-ordinates, bond lengths and bond angles were reported. High-resolution X-ray diffraction studies were carried out and good crystallinity for the grown crystal was observed from the diffraction curve. The grown crystals were subjected to dielectric studies. Ultraviolet-visible-near infrared spectralmore » analysis shows good optical transmission in the visible and infrared region of the grown crystals. The second harmonic generation efficiency of L-glutamic acid hydro bromide crystal was determined using the Kurtz powder test and it was found that it had efficiency comparable with that of the potassium di-hydrogen phosphate crystal.« less

Dilute antimonide nitride for long wavelength infrared photodetection

NASA Astrophysics Data System (ADS)

Chen, X. Z.; Jin, Y. J.; Zhang, D. H.

2014-05-01

InSb1-xNx materials were fabricated by direct nitrogen implantation into InSb wafer and they are characterized by X-ray diffraction, Hall measurement, X-ray photoelectron spectroscopy. In-N bonds are clearly demonstrated and other forms of nitrogen, such as antisites (NIn), interstitial N2, also exist in the grown films. The ratio to the total nitrogen bonds formed in the materials varies with preparation conditions. The optical bandgap data confirmed bandgap narrowing due to the incorporation of nitrogen. Photoconductive and photovoltaic photodetectors are fabricated and the cut-off frequencies of up to 11.5 μm are demonstrated.

Dilute antimonide nitride for long wavelength infrared photodetection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, X. Z.; Jin, Y. J.; Zhang, D. H.

2014-05-15

InSb{sub 1−x}N{sub x} materials were fabricated by direct nitrogen implantation into InSb wafer and they are characterized by X-ray diffraction, Hall measurement, X-ray photoelectron spectroscopy. In-N bonds are clearly demonstrated and other forms of nitrogen, such as antisites (N{sub In}), interstitial N{sub 2}, also exist in the grown films. The ratio to the total nitrogen bonds formed in the materials varies with preparation conditions. The optical bandgap data confirmed bandgap narrowing due to the incorporation of nitrogen. Photoconductive and photovoltaic photodetectors are fabricated and the cut-off frequencies of up to 11.5 μm are demonstrated.

X-ray diffraction and X-ray K absorption near edge studies of copper (II) complexes with amino acids

NASA Astrophysics Data System (ADS)

Sharma, P. K.; Mishra, Ashutosh; Malviya, Varsha; Kame, Rashmi; Malviya, P. K.

2017-05-01

Synthesis of copper (II) complexes [CuL1L2X].nH2O, where n=1, 2,3 (X=Cl,Br,NO3) (L1is 2,2’-bipyridine and L2 is L-tyrosine) by the chemical root method. The XRD data for the samples have been recorded. EXAFS spectra have also been recorded at the K-edge of Cu using the dispersive beam line BL-8 at 2.5 Gev Indus-2 Synchrotron radiation source at RRCAT, Indore, India. XRD and EXAFS data have been analysed using the computer software. X-ray diffraction studies of all complexes indicate their crystalline nature. Lattice parameter, bond length, particle size have been determined from XRD data.

Reintroducing electrostatics into macromolecular crystallographic refinement: application to neutron crystallography and DNA hydration.

PubMed

Fenn, Timothy D; Schnieders, Michael J; Mustyakimov, Marat; Wu, Chuanjie; Langan, Paul; Pande, Vijay S; Brunger, Axel T

2011-04-13

Most current crystallographic structure refinements augment the diffraction data with a priori information consisting of bond, angle, dihedral, planarity restraints, and atomic repulsion based on the Pauli exclusion principle. Yet, electrostatics and van der Waals attraction are physical forces that provide additional a priori information. Here, we assess the inclusion of electrostatics for the force field used for all-atom (including hydrogen) joint neutron/X-ray refinement. Two DNA and a protein crystal structure were refined against joint neutron/X-ray diffraction data sets using force fields without electrostatics or with electrostatics. Hydrogen-bond orientation/geometry favors the inclusion of electrostatics. Refinement of Z-DNA with electrostatics leads to a hypothesis for the entropic stabilization of Z-DNA that may partly explain the thermodynamics of converting the B form of DNA to its Z form. Thus, inclusion of electrostatics assists joint neutron/X-ray refinements, especially for placing and orienting hydrogen atoms. Copyright © 2011 Elsevier Ltd. All rights reserved.

Reintroducing Electrostatics into Macromolecular Crystallographic Refinement: Application to Neutron Crystallography and DNA Hydration

PubMed Central

Fenn, Timothy D.; Schnieders, Michael J.; Mustyakimov, Marat; Wu, Chuanjie; Langan, Paul; Pande, Vijay S.; Brunger, Axel T.

2011-01-01

Summary Most current crystallographic structure refinements augment the diffraction data with a priori information consisting of bond, angle, dihedral, planarity restraints and atomic repulsion based on the Pauli exclusion principle. Yet, electrostatics and van der Waals attraction are physical forces that provide additional a priori information. Here we assess the inclusion of electrostatics for the force field used for all-atom (including hydrogen) joint neutron/X-ray refinement. Two DNA and a protein crystal structure were refined against joint neutron/X-ray diffraction data sets using force fields without electrostatics or with electrostatics. Hydrogen bond orientation/geometry favors the inclusion of electrostatics. Refinement of Z-DNA with electrostatics leads to a hypothesis for the entropic stabilization of Z-DNA that may partly explain the thermodynamics of converting the B form of DNA to its Z form. Thus, inclusion of electrostatics assists joint neutron/X-ray refinements, especially for placing and orienting hydrogen atoms. PMID:21481775

First principles simulation of amorphous InSb

NASA Astrophysics Data System (ADS)

Los, Jan H.; Kühne, Thomas D.; Gabardi, Silvia; Bernasconi, Marco

2013-05-01

Ab initio molecular dynamics simulations based on density functional theory have been performed to generate a model of amorphous InSb by quenching from the melt. The resulting network is mostly tetrahedral with a minor fraction (10%) of atoms in a fivefold coordination. The structural properties are in good agreement with available x-ray diffraction and extended x-ray-absorption fine structure data and confirm the proposed presence of a sizable fraction of homopolar In-In and Sb-Sb bonds whose concentration in our model amounts to about 20% of the total number of bonds.

Near-neighbor mixing and bond dilation in mechanically alloyed Cu-Fe

NASA Astrophysics Data System (ADS)

Harris, V. G.; Kemner, K. M.; Das, B. N.; Koon, N. C.; Ehrlich, A. E.; Kirkland, J. P.; Woicik, J. C.; Crespo, P.; Hernando, A.; Garcia Escorial, A.

1996-09-01

Extended x-ray-absorption fine-structure (EXAFS) measurements were used to obtain element-specific, structural, and chemical information of the local environments around Cu and Fe atoms in high-energy ball-milled CuxFe1-x samples (x=0.50 and 0.70). Analysis of the EXAFS data shows both Fe and Cu atoms reside in face-centered-cubic sites where the first coordination sphere consists of a mixture of Fe and Cu atoms in a ratio which reflects the as-prepared stoichiometry. The measured bond distances indicate a dilation in the bonds between unlike neighbors which accounts for the lattice expansion measured by x-ray diffraction. These results indicate that metastable alloys having a positive heat of mixing can be prepared via the high-energy ball-milling process.

Multifunctional Metallosupramolecular Materials

DTIC Science & Technology

2011-02-28

supramolecular polymers based on 16 and Zn(NTf2)2 using small- angle X - ray scattering (SAXS) and transmission electron microscopy (TEM), carried out by...The SAXS data (Figure 13a) show multiple strong Bragg diffraction maxima at integer multiples of the scattering vector of the primary diffraction ...a minor amount of residual double bonds in the poly(ethylene-co-butylene) core. The metallopolymers 16·[Zn(NTf2)2] x exhibit similar traces, but do

Glass transition in ferroic glass K x (ND4)1-x D2PO4: a complete x-ray diffraction line shape analysis

NASA Astrophysics Data System (ADS)

Ranjan Choudhury, Rajul; Chitra, R.; Jayakrishnan, V. B.

2016-03-01

Quenching of dynamic disorder in glassy systems is termed as the glass transition. Ferroic glasses belong to the class of paracrystalline materials having crystallographic order in-between that of a perfect crystal and amorphous material, a classic example of ferroic glass is the solid solution of ferroelectric deuterated potassium dihydrogen phosphate and antiferroelectric deuterated ammonium dihydrogen phosphate. Lowering temperature of this ferroic glass can lead to a glass transition to a quenched disordered state. The subtle atomic rearrangement that takes place at such a glass transition can be revealed by careful examination of the temperature induced changes occurring in the x-ray powder diffraction (XRD) patterns of these materials. Hence we report here results of a complete diffraction line shape analysis of the XRD patterns recorded at different temperatures from deuterated mixed crystals DK x A1-x DP with mixing concentration x ranging as 0 < x < 1. Changes observed in diffraction peak shapes have been explained on the basis of structural rearrangements induced by changing O-D-O hydrogen bond dynamics in these paracrystals.

Correlated oxygen displacements and phonon mode changes in LaCoO3 single crystal

NASA Astrophysics Data System (ADS)

Sikolenko, V. V.; Molodtsov, S. L.; Izquierdo, M.; Troyanchuk, I. O.; Karpinsky, D.; Tiutiunnikov, S. I.; Efimova, E.; Prabhakaran, D.; Novoselov, D.; Efimov, V.

2018-05-01

X-ray diffraction and inelastic X-ray scattering studies have been performed across the spin ( 100 K) and semiconductor-metal ( 500 K) transitions in LaCoO3 single crystals. The quadratic increase with temperature of the oxygen displacement parameters parallel and perpendicular to the Co-O bond has been correlated with softening of the TO2 and hardening of the TO1 phonon branches along the [0 ξ ξ] high symmetry direction. The latter effect can be associated with the weakening of the Co-O bond strength derived from the increase of Co-O bond length and angle as expected upon increasing the high spin state population of the system with temperature.

Synthesis and the crystal and molecular structure of the germanium(IV) complex with propylene-1,3-diaminetetraacetic acid [Ge(Pdta)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sergienko, V. S., E-mail: sergienko@igic.ras.ru; Martsinko, E. E.; Seifullina, I. I.

2015-09-15

The germanium(IV) complex with propylene-1,3-diaminetetraacetic acid (H{sub 4}Pdta) is studied by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. The X-ray diffraction study reveals two crystallographically independent [Ge(Pdta)] molecules of similar structure. Both Ge atoms are octahedrally coordinated by four O atoms and two N atoms (at the cis positions) of the hexadentate pentachelate Pdta{sup 4–} ligand. An extended system of weak C—H···O hydrogen bonds connects complex molecules into a supramolecular 3D framework.

Synthesis and the crystal and molecular structure of the germanium(IV) complex with propylene-1,3-diaminetetraacetic acid [Ge( Pdta)

NASA Astrophysics Data System (ADS)

Sergienko, V. S.; Martsinko, E. E.; Seifullina, I. I.; Churakov, A. V.; Chebanenko, E. A.

2015-09-01

The germanium(IV) complex with propylene-1,3-diaminetetraacetic acid (H4 Pdta) is studied by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. The X-ray diffraction study reveals two crystallographically independent [Ge( Pdta)] molecules of similar structure. Both Ge atoms are octahedrally coordinated by four O atoms and two N atoms (at the cis positions) of the hexadentate pentachelate Pdta 4- ligand. An extended system of weak С—Н···О hydrogen bonds connects complex molecules into a supramolecular 3D framework.

Hydrogen bonds directed 2D → 3D interdigitated Cd(II) compound: Synthesis, crystal structure and dual-emission luminescent properties

NASA Astrophysics Data System (ADS)

Yu, Yuanyuan

2017-06-01

A new Cd(II) compound, namely [Cd2(btc)(phen)2Cl]n·n(H2O)·n(DMA) (1, H3btc = 1, 3, 5-benzenetricarboxylic acid, phen = 1,10-phenanthroline, DMA = N,N'-dimethylacetamide) has been synthesized and structurally characterized by single-crystal X-ray diffraction analysis. This compound crystallizes in monoclinic P21/n space group with a = 13.5729(7) Å, b = 20.1049(7) Å, c = 13.9450(6) Å, β = 104.671(4)°, Z = 4. Single-crystal X-ray diffraction analysis reveals that compound 1 features a 2D → 3D interdigitated framework directed by the intermolecular hydrogen bonds. In addition, the luminescent properties of compound 1 were also investigated in the solid state at room temperature.

Insights into the mechanism of X-ray-induced disulfide-bond cleavage in lysozyme crystals based on EPR, optical absorption and X-ray diffraction studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sutton, Kristin A.; Black, Paul J.; Mercer, Kermit R.

2013-12-01

Electron paramagnetic resonance (EPR) and online UV–visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage, to confirm a multi-track radiation-damage process and to develop a model of that process. Electron paramagnetic resonance (EPR) and online UV–visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage. Online UV–visible spectroscopy showed that upon X-irradiation, disulfide radicalization appeared to saturate at an absorbed dose of approximately 0.5–0.8 MGy, in contrast to the saturating dose of ∼0.2 MGy observed using EPR at much lower dose rates. Themore » observations suggest that a multi-track model involving product formation owing to the interaction of two separate tracks is a valid model for radiation damage in protein crystals. The saturation levels are remarkably consistent given the widely different experimental parameters and the range of total absorbed doses studied. The results indicate that even at the lowest doses used for structural investigations disulfide bonds are already radicalized. Multi-track considerations offer the first step in a comprehensive model of radiation damage that could potentially lead to a combined computational and experimental approach to identifying when damage is likely to be present, to quantitate it and to provide the ability to recover the native unperturbed structure.« less

Bond compressibility and bond Grüneisen parameters of CdTe

NASA Astrophysics Data System (ADS)

Fornasini, P.; Grisenti, R.; Irifune, T.; Shinmei, T.; Mathon, O.; Pascarelli, S.; Rosa, A. D.

2018-06-01

Extended x-ray absorption fine structure (EXAFS) at the Cd K edge and diffraction patterns have been measured on CdTe as a function of pressure from 100 kPa (1 bar) to 5 GPa using a cell with nano-polycrystalline diamond anvils and an x-ray focussing scanning spectrometer. Three phases—zincblende (ZB), mixed cinnabar-ZB and rocksalt (RS)—are well distinguished in different pressure intervals. The bond compressibility measured by EXAFS in the ZB phase is slightly smaller than the one measured by diffraction and decreases significantly faster when the pressure increases; the difference is attributed to the effect of relative vibrations perpendicular to the Cd–Te bond. The parallel mean square relative displacement (MSRD) decreases, the perpendicular MSRD increases when the pressure increases, leading to an increasing anisotropy of relative atomic vibrations. A constant-temperature bond Grüneisen parameter (GP) has been evaluated for the ZB phase and compared with the constant-pressure bond GP measured in a previous experiment; an attempt is made to connect the bond GPs measured by EXAFS and the more familiar thermodynamic GP and mode GPs; the comparisons suggest the inadequacy of the quasi-harmonic approximation to deal with the local vibrational properties sampled by EXAFS.

1-Amino-4-hydroxy-9,10-anthraquinone - An analogue of anthracycline anticancer drugs, interacts with DNA and induces apoptosis in human MDA-MB-231 breast adinocarcinoma cells: Evaluation of structure-activity relationship using computational, spectroscopic and biochemical studies.

PubMed

Mondal, Palash; Roy, Sanjay; Loganathan, Gayathri; Mandal, Bitapi; Dharumadurai, Dhanasekaran; Akbarsha, Mohammad A; Sengupta, Partha Sarathi; Chattopadhyay, Shouvik; Guin, Partha Sarathi

2015-12-01

The X-ray diffraction and spectroscopic properties of 1-amino-4-hydroxy-9,10-anthraquinone (1-AHAQ), a simple analogue of anthracycline chemotherapeutic drugs were studied by adopting experimental and computational methods. The optimized geometrical parameters obtained from computational methods were compared with the results of X-ray diffraction analysis and the two were found to be in reasonably good agreement. X-ray diffraction study, Density Functional Theory (DFT) and natural bond orbital (NBO) analysis indicated two types of hydrogen bonds in the molecule. The IR spectra of 1-AHAQ were studied by Vibrational Energy Distribution Analysis (VEDA) using potential energy distribution (PED) analysis. The electronic spectra were studied by TDDFT computation and compared with the experimental results. Experimental and theoretical results corroborated each other to a fair extent. To understand the biological efficacy of 1-AHAQ, it was allowed to interact with calf thymus DNA and human breast adino-carcinoma cell MDA-MB-231. It was found that the molecule induces apoptosis in this adinocarcinoma cell, with little, if any, cytotoxic effect in HBL-100 normal breast epithelial cell.

Structural studies of the rhombohedral and orthorhombic monouranates: CaUO{sub 4}, α-SrUO{sub 4}, β-SrUO{sub 4} and BaUO{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murphy, Gabriel; Kennedy, Brendan J., E-mail: kennedyb@chem.usyd.edu.au; Johannessen, Bernt

The structures of some AUO{sub 4} (A=Ca, Sr, or Ba) oxides have been determined using a combination of neutron and synchrotron X-ray diffraction, supported by X-ray absorption spectroscopic measurements at the U L{sub 3}-edge. The smaller Ca cation favours a rhombohedral AUO{sub 4} structure with 8-coordinate UO{sub 8} moieties whilst an orthorhombic structure based on UO{sub 6} groups is found for BaUO{sub 4}. Both the rhombohedral and orthorhombic structures can be stabilised for SrUO{sub 4}. The structural studies suggest that the bonding requirements of the A site cation play a significant role in determining which structure is favoured. In themore » rhombohedral structure, Bond Valence Sums demonstrate the A site is invariably overbonded, which, in the case of rhombohedral α-SrUO{sub 4}, is compensated for by the formation of vacancies in the oxygen sub-lattice. The uranium cation, with its flexible oxidation state, is able to accommodate this by inducing vacancies along its equatorial coordination site as demonstrated by neutron powder diffraction. - Graphical abstract: Diffraction studies of AUO{sub 4} (A = Ca, Sr, or Ba) oxides reveal the importance of the bonding requirements of the A site cation in determining whether the structure is rhombohedral or orthorhombic. - Highlights: • Structures of AUO{sub 4} ( A = Ca Sr, Ba) refined against X-ray and Neutron diffraction. • The alkali cations size has a dramatic effect on the crystal structure. • Smaller cations favouring a rhombohedral structure. • Oxygen vacancies to stabilise the rhombohedral structure in SrUO{sub 4}.« less

Integrated in-situ probes for structural and dynamic properties of geological materials at ultrahigh pressures and temperatures

NASA Astrophysics Data System (ADS)

Mao, H.; Mao, W. L.

2005-12-01

Multiple x-ray and allied probes have been recently developed and integrated with diamond-anvil cells at synchrotron facilities. They have effectively opened up the vast field area of the Earth's interior to direct, in-situ study. For instance, x-ray emission spectroscopy identifies the high-spin-low-spin transition that governs Fe-Mg partitioning, the most important factor in element differentiation in the mantle. Inelastic x-ray near-edge spectroscopy reveals the bonding nature of light elements that control the phase transitions, structure and partitioning of these elements (e.g., carbon bonding changes as an element, and in oxides, carbonates, and silicates). X-ray diffraction combined with laser-heated diamond anvil cell determines crystal structures and P-V-T equations of state. Shear moduli, single-crystal elasticity, and phonon dynamics can be measured to the core pressures with newly-enabled, complementary techniques, including radial x-ray diffraction, nuclear resonant inelastic x-ray scattering, non-resonant inelastic x-ray scattering, high-temperature Raman spectroscopy, and Brillouin scattering spectroscopy. The nonhydrostatic stress in solid samples which was previously regarded as a nuisance that degraded the experiments, can now be used for extracting important rheological information, including deformation mechanisms, preferred orientation, slip systems, plasticity, failure, and shear strength of major mantle and core minerals at high pressures. With the new arsenal of experimental techniques over the extended P-T-x regimes at we can now address questions that were not conceivable only a decade ago. Knowledge of the high P-T properties is leading to fundamental improvements in interpreting seismological observations and understanding the structure, dynamics, and evolution of the Earth's deep interior.

Probing the thermal stability and the decomposition mechanism of a magnesium-fullerene polymer via X-ray Raman spectroscopy, X-ray diffraction and molecular dynamics simulations.

PubMed

Aramini, Matteo; Niskanen, Johannes; Cavallari, Chiara; Pontiroli, Daniele; Musazay, Abdurrahman; Krisch, Michael; Hakala, Mikko; Huotari, Simo

2016-02-21

We report the microscopic view of the thermal structural stability of the magnesium intercalated fullerene polymer Mg2C60. With the application of X-ray Raman spectroscopy and X-ray diffraction, we study in detail the decomposition pathways of the polymer system upon annealing at temperatures between 300 and 700 °C. We show that there are at least two energy scales involved in the decomposition reaction. Intermolecular carbon bonds, which are responsible for the formation of a 2D fullerene polymer, are broken with a relatively modest thermal energy, while the long-range order of the original polymer remains intact. With an increased thermal energy, the crystal structure in turn is found to undergo a transition to a novel intercalated cubic phase that is stable up to the highest temperature studied here. The local structure surrounding magnesium ions gets severely modified close to, possibly at, the phase transition. We used density functional theory based calculations to study the thermodynamic and kinetic aspects of the collapse of the fullerene network, and to explain the intermediate steps as well as the reaction pathways in the break-up of this peculiar C60 intermolecular bonding architecture.

Synchrotron X-ray diffraction study of the Ba{sub 1−x}SrSnO{sub 3} solid solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prodjosantoso, Anti K., E-mail: Prodjosantoso@yahoo.com; Zhou, Qingdi; Kennedy, Brendan J.

At room temperature the sequence of phases with increasing amounts of strontium in the stannate perovskite system Ba{sub 1−x}SrSnO{sub 3} has been established from high resolution synchrotron X-ray powder diffraction. The observed sequence orthorhombic (Pbnm), orthorhombic (Ibmm), tetragonal (I4/mcm), and cubic (Pm3-bar m) is a consequence of the sequential introduction of cooperative tilting of the corner sharing SnO{sub 6} octahedra. The cell volume changes smoothly across the series with no obvious discontinuities associated with the phase transitions. - Graphical abstract: Portions of the synchrotron X-ray diffraction profiles (λ=0.82453 Å) from selected Ba{sub 1−x}Sr{sub x}SnO{sub 3} samples together with the resultsmore » of fitting by the Rietveld method. Highlights: ► Structures of the stannate perovskites Ba{sub 1−x}SrSnO{sub 3} refined from synchrotron XRD. ► The sequence Pm3-bar m→I4/mcm→Ibmm→Pbnm results from tilting of the octahedra. ► The tilting maintains optimal bonding of the cations seen from the BVS analysis.« less

Tetraalkylammonium Salts as Hydrogen-Bonding Catalysts.

PubMed

Shirakawa, Seiji; Liu, Shiyao; Kaneko, Shiho; Kumatabara, Yusuke; Fukuda, Airi; Omagari, Yumi; Maruoka, Keiji

2015-12-21

Although the hydrogen-bonding ability of the α hydrogen atoms on tetraalkylammonium salts is often discussed with respect to phase-transfer catalysts, catalysis that utilizes the hydrogen-bond-donor properties of tetraalkylammonium salts remains unknown. Herein, we demonstrate hydrogen-bonding catalysis with newly designed tetraalkylammonium salt catalysts in Mannich-type reactions. The structure and the hydrogen-bonding ability of the new ammonium salts were investigated by X-ray diffraction analysis and NMR titration studies. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tripathi, S., E-mail: shilpatr3@gmail.com; Shripathi, T.; Tripathi, J.

The results are reported on solution cast PMMA-PCTFE blend films characterized using x-ray diffraction and FTIR. The nanocrystalline nature of PMMA is still seen in the blends, however, the bond modifications are clearly observed. The addition of PCTFE results in the modification in structural properties, as reflected in the XRD and FTIR spectra showing modifications in bonding as a function of PCTFE percentage.

Structure, Elastic Constants and XRD Spectra of Extended Solids under High Pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Batyrev, I. G.; Coleman, S. P.; Ciezak-Jenkins, J. A.

We present results of evolutionary simulations based on density functional calculations of a potentially new type of energetic materials called extended solids: P-N and N-H. High-density structures with covalent bonds generated using variable and fixed concentration methods were analysed in terms of thermo-dynamical stability and agreement with experimental X-ray diffraction (XRD) spectra. X-ray diffraction spectra were calculated using a virtual diffraction algorithm that computes kinematic diffraction intensity in three-dimensional reciprocal space before being reduced to a two-theta line profile. Calculated XRD patterns were used to search for the structure of extended solids present at experimental pressures by optimizing data accordingmore » to experimental XRD peak position, peak intensity and theoretically calculated enthalpy. Elastic constants has been calculated for thermodynamically stable structures of P-N system.« less

Crystal structure of pentasodium hydrogen dicitrate from synchrotron X-ray powder diffraction data and DFT comparison

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rammohan, Alagappa; Kaduk, James A.

2017-01-27

The crystal structure of pentasodium hydrogen dicitrate, Na 5H(C 6H 5O 7) 2, has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Each of the two independent citrate anions is joined into a dimer by very strong centrosymmetric O—H...O hydrogen bonds, with O...O distances of 2.419 and 2.409 Å. Four octahedrally coordinated Na +ions share edges to form open layers parallel to theabplane. A fifth Na +ion in trigonal–bipyramidal coordination shares faces with NaO 6octahedra on both sides of these layers.

Insights into the mechanism of X-ray-induced disulfide-bond cleavage in lysozyme crystals based on EPR, optical absorption and X-ray diffraction studies.

PubMed

Sutton, Kristin A; Black, Paul J; Mercer, Kermit R; Garman, Elspeth F; Owen, Robin L; Snell, Edward H; Bernhard, William A

2013-12-01

Electron paramagnetic resonance (EPR) and online UV-visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage. Online UV-visible spectroscopy showed that upon X-irradiation, disulfide radicalization appeared to saturate at an absorbed dose of approximately 0.5-0.8 MGy, in contrast to the saturating dose of ∼0.2 MGy observed using EPR at much lower dose rates. The observations suggest that a multi-track model involving product formation owing to the interaction of two separate tracks is a valid model for radiation damage in protein crystals. The saturation levels are remarkably consistent given the widely different experimental parameters and the range of total absorbed doses studied. The results indicate that even at the lowest doses used for structural investigations disulfide bonds are already radicalized. Multi-track considerations offer the first step in a comprehensive model of radiation damage that could potentially lead to a combined computational and experimental approach to identifying when damage is likely to be present, to quantitate it and to provide the ability to recover the native unperturbed structure.

Taking Snapshots of Photosynthetic Water Oxidation Using Femtosecond X-ray Diffraction and Spectroscopy

PubMed Central

Kern, Jan; Tran, Rosalie; Alonso-Mori, Roberto; Koroidov, Sergey; Echols, Nathaniel; Hattne, Johan; Ibrahim, Mohamed; Gul, Sheraz; Laksmono, Hartawan; Sierra, Raymond G.; Gildea, Richard J.; Han, Guangye; Hellmich, Julia; Lassalle-Kaiser, Benedikt; Chatterjee, Ruchira; Brewster, Aaron S.; Stan, Claudiu A.; Glöckner, Carina; Lampe, Alyssa; DiFiore, Dörte; Milathianaki, Despina; Fry, Alan R.; Seibert, M. Marvin; Koglin, Jason E.; Gallo, Erik; Uhlig, Jens; Sokaras, Dimosthenis; Weng, Tsu-Chien; Zwart, Petrus H.; Skinner, David E.; Bogan, Michael J.; Messerschmidt, Marc; Glatzel, Pieter; Williams, Garth J.; Boutet, Sébastien; Adams, Paul D.; Zouni, Athina; Messinger, Johannes; Sauter, Nicholas K.; Bergmann, Uwe; Yano, Junko; Yachandra, Vittal K.

2014-01-01

The dioxygen we breathe is formed from water by its light-induced oxidation in photosystem II. O2 formation takes place at a catalytic manganese cluster within milliseconds after the photosystem II reaction center is excited by three single-turnover flashes. Here we present combined X-ray emission spectra and diffraction data of 2 flash (2F) and 3 flash (3F) photosystem II samples, and of a transient 3F′ state (250 μs after the third flash), collected under functional conditions using an X-ray free electron laser. The spectra show that the initial O-O bond formation, coupled to Mn-reduction, does not yet occur within 250 μs after the third flash. Diffraction data of all states studied exhibit an anomalous scattering signal from Mn but show no significant structural changes at the present resolution of 4.5 Å. This study represents the initial frames in a molecular movie of the structural changes during the catalytic reaction in photosystem II. PMID:25006873

Studies on the growth, structural, spectral and third-order nonlinear optical properties of ammonium 3-carboxy-4-hydroxy benzenesulfonate monohydrate single crystal.

PubMed

Silambarasan, A; Krishna Kumar, M; Thirunavukkarasu, A; Mohan Kumar, R; Umarani, P R

2015-01-25

An organic nonlinear optical bulk single crystal, Ammonium 3-carboxy-4-hydroxy benzenesulfonate monohydrate (ACHBS) was successfully grown by solution growth technique. Single crystal X-ray diffraction study confirms that, the grown crystal belongs to P21/c space group. Powder X-ray diffraction and high resolution X-ray diffraction analyses revealed the crystallinity of the grown crystal. Infrared spectral analysis showed the vibrational behavior of chemical bonds and its functional groups. The thermal stability and decomposition stages of the grown crystal were studied by TG-DTA analysis. UV-Visible transmittance studies showed the transparency region and cut-off wavelength of the grown crystal. The third-order nonlinear optical susceptibility of the grown crystal was estimated by Z-scan technique using He-Ne laser source. The mechanical property of the grown crystal was studied by using Vicker's microhardness test. Copyright © 2014 Elsevier B.V. All rights reserved.

Taking snapshots of photosynthetic water oxidation using femtosecond X-ray diffraction and spectroscopy

NASA Astrophysics Data System (ADS)

Kern, Jan; Tran, Rosalie; Alonso-Mori, Roberto; Koroidov, Sergey; Echols, Nathaniel; Hattne, Johan; Ibrahim, Mohamed; Gul, Sheraz; Laksmono, Hartawan; Sierra, Raymond G.; Gildea, Richard J.; Han, Guangye; Hellmich, Julia; Lassalle-Kaiser, Benedikt; Chatterjee, Ruchira; Brewster, Aaron S.; Stan, Claudiu A.; Glöckner, Carina; Lampe, Alyssa; Difiore, Dörte; Milathianaki, Despina; Fry, Alan R.; Seibert, M. Marvin; Koglin, Jason E.; Gallo, Erik; Uhlig, Jens; Sokaras, Dimosthenis; Weng, Tsu-Chien; Zwart, Petrus H.; Skinner, David E.; Bogan, Michael J.; Messerschmidt, Marc; Glatzel, Pieter; Williams, Garth J.; Boutet, Sébastien; Adams, Paul D.; Zouni, Athina; Messinger, Johannes; Sauter, Nicholas K.; Bergmann, Uwe; Yano, Junko; Yachandra, Vittal K.

2014-07-01

The dioxygen we breathe is formed by light-induced oxidation of water in photosystem II. O2 formation takes place at a catalytic manganese cluster within milliseconds after the photosystem II reaction centre is excited by three single-turnover flashes. Here we present combined X-ray emission spectra and diffraction data of 2-flash (2F) and 3-flash (3F) photosystem II samples, and of a transient 3F’ state (250 μs after the third flash), collected under functional conditions using an X-ray free electron laser. The spectra show that the initial O-O bond formation, coupled to Mn reduction, does not yet occur within 250 μs after the third flash. Diffraction data of all states studied exhibit an anomalous scattering signal from Mn but show no significant structural changes at the present resolution of 4.5 Å. This study represents the initial frames in a molecular movie of the structural changes during the catalytic reaction in photosystem II.

Synthesis and X-ray crystal structure determination of N- p-methylphenyl-4-benzoyl-3,4-diphenyl-2-azetidinone

NASA Astrophysics Data System (ADS)

Kabak, Mehmet; Şenöz, Hülya; Elmali, Ayhan; Adar, Vildan; Svoboda, Ingrid; Dušek, Michal; Fejfarová, Karla

2010-12-01

The title compound, C29H23NO2, has been characterized by single-crystal X-ray diffraction at two different temperatures (303 K and 120 K) and wavelengths (Mo K α and Cu K α). The non-centrosymmetric hexagonal crystal structure contains four-membered planar β-lactam ring with an unusually long C-C bond. The β-lactam ring is almost planar.

Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy.

PubMed

Oh, Sang Youn; Yoo, Dong Il; Shin, Younsook; Kim, Hwan Chul; Kim, Hak Yong; Chung, Yong Sik; Park, Won Ho; Youk, Ji Ho

2005-10-31

Crystalline structures of cellulose (named as Cell 1), NaOH-treated cellulose (Cell 2), and subsequent CO2-treated cellulose (Cell 2-C) were analyzed by wide-angle X-ray diffraction and FTIR spectroscopy. Transformation from cellulose I to cellulose II was observed by X-ray diffraction for Cell 2 treated with 15-20 wt% NaOH. Subsequent treatment with CO2 also transformed the Cell 2-C treated with 5-10 wt% NaOH. Many of the FTIR bands including 2901, 1431, 1282, 1236, 1202, 1165, 1032, and 897 cm(-1) were shifted to higher wave number (by 2-13 cm(-1)). However, the bands at 3352, 1373, and 983 cm(-1) were shifted to lower wave number (by 3-95 cm(-1)). In contrast to the bands at 1337, 1114, and 1058 cm(-1), the absorbances measured at 1263, 993, 897, and 668 cm(-1) were increased. The FTIR spectra of hydrogen-bonded OH stretching vibrations at around 3352 cm(-1) were resolved into three bands for cellulose I and four bands for cellulose II, assuming that all the vibration modes follow Gaussian distribution. The bands of 1 (3518 cm(-1)), 2 (3349 cm(-1)), and 3 (3195 cm(-1)) were related to the sum of valence vibration of an H-bonded OH group and an intramolecular hydrogen bond of 2-OH ...O-6, intramolecular hydrogen bond of 3-OH...O-5 and the intermolecular hydrogen bond of 6-O...HO-3', respectively. Compared with the bands of cellulose I, a new band of 4 (3115 cm(-1)) related to intermolecular hydrogen bond of 2-OH...O-2' and/or intermolecular hydrogen bond of 6-OH...O-2' in cellulose II appeared. The crystallinity index (CI) was obtained by X-ray diffraction [CI(XD)] and FTIR spectroscopy [CI(IR)]. Including absorbance ratios such as A1431,1419/A897,894 and A1263/A1202,1200, the CI(IR) was evaluated by the absorbance ratios using all the characteristic absorbances of cellulose. The CI(XD) was calculated by the method of Jayme and Knolle. In addition, X-ray diffraction curves, with and without amorphous halo correction, were resolved into portions of cellulose I and cellulose II lattice. From the ratio of the peak area, that is, peak area of cellulose I (or cellulose II)/total peak area, CI(XD) were divided into CI(XD-CI) for cellulose I and CI(XD-CII) for cellulose II. The correlation between CI(XD-CI) (or CI(XD-CII)) and CI(IR) was evaluated, and the bands at 2901 (2802), 1373 (1376), 897 (894), 1263, 668 cm(-1) were good for the internal standard (or denominator) of CI(IR), which increased the correlation coefficient. Both fraction of the absorbances showing peak shift were assigned as the alternate components of CI(IR). The crystallite size was decreased to constant value for Cell 2 treated at >or= 15 wt% NaOH. The crystallite size of Cell 2-C (cellulose II) was smaller than that of Cell 2 (cellulose I) treated at 5-10 wt% NaOH. But the crystallite size of Cell 2-C (cellulose II) was larger than that of Cell 2 (cellulose II) treated at 15-20 wt% NaOH.

Part II: diffraction from two-dimensional cholera toxin crystals bound to their receptors in a lipid monolayer.

PubMed

Miller, C E; Majewski, J; Watkins, E B; Weygand, M; Kuhl, T L

2008-07-01

The structure of cholera toxin (CTAB(5)) bound to its putative ganglioside receptor, galactosyl-N-acetylgalactosaminyl (N-acetyl-neuraminyl) galactosylglucosylceramide (GM(1)), in a lipid monolayer at the air-water interface has been studied utilizing grazing incidence x-ray diffraction. Cholera toxin is one of very few proteins to be crystallized in two dimensions and characterized in a fully hydrated state. The observed grazing incidence x-ray diffraction Bragg peaks indicated cholera toxin was ordered in a hexagonal lattice and the order extended 600-800 A. The pentameric binding portion of cholera toxin (CTB(5)) improved in-plane ordering over the full toxin (CTAB(5)) especially at low pH. Disulfide bond reduction (activation of the full toxin) also increased the protein layer ordering. These findings are consistent with A-subunit flexibility and motion, which cause packing inefficiencies and greater disorder of the protein layer. Corroborative out-of-plane diffraction (Bragg rod) analysis indicated that the scattering units in the cholera layer with CTAB(5) shortened after disulfide bond reduction of the A subunit. These studies, together with Part I results, revealed key changes in the structure of the cholera toxin-lipid system under different pH conditions.

Relaxation processes in disaccharide sugar glasses

NASA Astrophysics Data System (ADS)

Hwang, Yoon-Hwae; Kwon, Hyun-Joung; Seo, Jeong-Ah; Shin, Dong-Myeong; Ha, Ji-Hye; Kim, Hyung-Kook

2013-02-01

We represented relaxation processes of disaccharide sugars (anhydrous trehalose and maltose) in supercooled and glassy states by using several spectroscopy techniques which include a broadband dielectric loss spectroscopy, photon correlation spectroscopy and X-ray diffraction (Retvield analysis) methods which are powerful tools to measure the dynamics in glass forming materials. In a dielectric loss spectroscopy study, we found that anhydrous trehalose and maltose glasses have an extra relaxation process besides α-, JG β- and γ-relaxations which could be related to a unique property of glycoside bond in disaccharides. In photon correlation spectroscopy study, we found an interesting compressed exponential relaxation at temperatures above 140°C. The q-1 dependence of its relaxation time corresponds to an ultraslow ballistic motion due to the local structure rearrangements. In the same temperature range, we found the glycosidic bond structure changes in trehalose molecule from the Raman and the Retvield X-ray diffraction measurements indicating that the observed compressed exponential relaxation in supercooled liquid trehalose could be resulted in the glycosidic bond structure change. Therefore, the overall results from this study might support the fact that the superior bioprotection ability of disaccharide sugar glasses might originate from this unique relaxation process of glycosidic bond.

X-ray-induced dissociation of H.sub.2O and formation of an O.sub.2-H.sub.2 alloy at high pressure

DOEpatents

Mao, Ho-kwang [Washington, DC; Mao, Wendy L [Washington, DC

2011-11-29

A novel molecular alloy of O.sub.2 and H.sub.2 and a method of producing such a molecular alloy are provided. When subjected to high pressure and extensive x-radiation, H.sub.2O molecules cleaved, forming O--O and H--H bonds. In the method of the present invention, the O and H framework in ice VII was converted into a molecular alloy of O.sub.2 and H.sub.2. X-ray diffraction, x-ray Raman scattering, and optical Raman spectroscopy demonstrate that this crystalline solid differs from previously known phases.

Digital model for X-ray diffraction with application to composition and strain determination in strained InAs/GaSb superlattices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meng, Yifei; Kim, Honggyu; Zuo, Jian-Min

2014-07-07

We propose a digital model for high quality superlattices by including fluctuations in the superlattice periods. The composition and strain profiles are assumed to be coherent and persist throughout the superlattice. Using this model, we have significantly improved the fit with experimental X-ray diffraction data recorded from the nominal InAs/GaSb superlattice. The lattice spacing of individual layers inside the superlattice and the extent of interfacial intermixing are refined by including both (002) and (004) and their satellite peaks in the fitting. For the InAs/GaSb strained layer superlattice, results show: (i) the GaSb-on-InAs interface is chemically sharper than the InAs-on-GaSb interface,more » (ii) the GaSb layers experience compressive strain with In incorporation, (iii) there are interfacial strain associated with InSb-like bonds in GaSb and GaAs-like bonds in InAs, (iv) Sb substitutes a significant amount of In inside InAs layer near the InAs-on-GaSb interface. For support, we show that the composition profiles determined by X-ray diffraction are in good agreement with those obtained from atom probe tomography measurement. Comparison with the kinetic growth model shows a good agreement in terms of the composition profiles of anions, while the kinetic model underestimates the intermixing of cations.« less

Exploring Orthogonal Hydrogen Bonding towards Designing Organic-Salt-Based Supramolecular Gelators: Synthesis, Structures, and Anticancer Properties.

PubMed

Chakraborty, Poulami; Dastidar, Parthasarathi

2018-05-18

A series of primary ammonium monocarboxylate (PAM) salts derived from β-alanine derivatives of pyrene and naphthalene acetic acid, along with the parent acids, were explored to probe the plausible role of orthogonal hydrogen bonding resulting from amide⋅⋅⋅amide and PAM synthons on gelation. Single-crystal X-ray diffraction (SXRD) studies were performed on two parent acids and five PAM salts in the series. The data revealed that orthogonal hydrogen bonding played an important role in gelation. Structure-property correlation based on SXRD and powder X-ray diffraction data also supported the working hypothesis upon which these gelators were designed. 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and cell migration assay on a highly aggressive human breast cancer cell line, MDA-MB-231, revealed that one of the PAM salts in the series, namely, PAA.B2, displayed anticancer properties, and internalization of the gelator salt in the same cell line was confirmed by cell imaging. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chuvashova, Irina, E-mail: irina.chuvashova@gmail.com; Bayerisches Geoinstitut, University of Bayreuth, D-95440 Bayreuth; Bykova, Elena

In the present study single crystals of rhombohedral α-B were investigated under pressure to 60 GPa by means of single-crystal X-ray diffraction. The bulk modulus of α-B was found to be K=224(7) GPa (K′=3.0(3)). Measurements of interatomic distances as a function of pressure revealed that the intericosahedral two-center two-electron (2c–2e) bonds are almost as stiff as some of intraicosahedral ones. The three-center two-electron (3c–2e) intericosahedral bonds show much higher compliance compared to other bonds in α-B. The vibrational properties of α-B under pressure were investigated by Raman spectroscopy at pressures up to 160 GPa and IR spectroscopy at pressures upmore » to 53 GPa. - Graphical abstract: The rhombohedral α-B is highly incompressible and extremely stable: it maintains its crystal structure up to 160 GPa and its intericosahedral 2e2c bonds are almost as stiff as some of intraicosahedral ones. - Highlights: • Structural stability of α-B has been investigated up to 160 GPa on single crystals. • Single-crystal x-ray diffraction reveals that α-B is highly incompressible. • Compressibility of B{sub 12} icosahedra is considerably lower than that of the bulk material. • Intericosahedral 2e2c bonds are almost as stiff as some of intraicosahedral ones.« less

Effect of oxygen incorporation on the structure and elasticity of Ti-Al-O-N coatings synthesized by cathodic arc and high power pulsed magnetron sputtering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hans, M., E-mail: hans@mch.rwth-aachen.de; Baben, M. to; Music, D.

2014-09-07

Ti-Al-O-N coatings were synthesized by cathodic arc and high power pulsed magnetron sputtering. The chemical composition of the coatings was determined by means of elastic recoil detection analysis and energy dispersive X-ray spectroscopy. The effect of oxygen incorporation on the stress-free lattice parameters and Young's moduli of Ti-Al-O-N coatings was investigated by X-ray diffraction and nanoindentation, respectively. As nitrogen is substituted by oxygen, implications for the charge balance may be expected. A reduction in equilibrium volume with increasing O concentration is identified by X-ray diffraction and density functional theory calculations of Ti-Al-O-N supercells reveal the concomitant formation of metal vacancies.more » Hence, the oxygen incorporation-induced formation of metal vacancies enables charge balancing. Furthermore, nanoindentation experiments reveal a decrease in elastic modulus with increasing O concentration. Based on ab initio data, two causes can be identified for this: First, the metal vacancy-induced reduction in elasticity; and second, the formation of, compared to the corresponding metal nitride bonds, relatively weak Ti-O and Al-O bonds.« less

White-beam X-ray diffraction and radiography studies on high-boron-containing borosilicate glass at high pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ham, Kathryn J.; Vohra, Yogesh K.; Kono, Yoshio

Multi-angle energy-dispersive X-ray diffraction studies and white-beam X-ray radiography were conducted with a cylindrically shaped (1 mm diameter and 0.7 mm high) high-boron-content borosilicate glass sample (17.6% B 2O 3) to a pressure of 13.7 GPa using a Paris-Edinburgh (PE) press at Beamline 16-BM-B, HPCAT of the Advanced Photon Source. The measured structure factor S(q) to large q = 19 Å –1 is used to determine information about the internuclear bond distances between various species of atoms within the glass sample. Sample pressure was determined with gold as a pressure standard. The sample height as measured by radiography showed anmore » overall uniaxial compression of 22.5% at 13.7 GPa with 10.6% permanent compaction after decompression to ambient conditions. The reduced pair distribution function G(r) was extracted and Si–O, O–O and Si–Si bond distances were measured as a function of pressure. Lastly, Raman spectroscopy of the pressure recovered sample as compared to starting material showed blue-shift and changes in intensity and widths of Raman bands associated with silicate and four-coordinated boron.« less

White-beam X-ray diffraction and radiography studies on high-boron-containing borosilicate glass at high pressures

DOE PAGES

Ham, Kathryn J.; Vohra, Yogesh K.; Kono, Yoshio; ...

2017-02-06

Multi-angle energy-dispersive X-ray diffraction studies and white-beam X-ray radiography were conducted with a cylindrically shaped (1 mm diameter and 0.7 mm high) high-boron-content borosilicate glass sample (17.6% B 2O 3) to a pressure of 13.7 GPa using a Paris-Edinburgh (PE) press at Beamline 16-BM-B, HPCAT of the Advanced Photon Source. The measured structure factor S(q) to large q = 19 Å –1 is used to determine information about the internuclear bond distances between various species of atoms within the glass sample. Sample pressure was determined with gold as a pressure standard. The sample height as measured by radiography showed anmore » overall uniaxial compression of 22.5% at 13.7 GPa with 10.6% permanent compaction after decompression to ambient conditions. The reduced pair distribution function G(r) was extracted and Si–O, O–O and Si–Si bond distances were measured as a function of pressure. Lastly, Raman spectroscopy of the pressure recovered sample as compared to starting material showed blue-shift and changes in intensity and widths of Raman bands associated with silicate and four-coordinated boron.« less

Toward Design Principles for Diffusionless Transformations: The Frustrated Formation of Co–Co Bonds in a Low-Temperature Polymorph of GdCoSi 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vinokur, Anastasiya I.; Fredrickson, Daniel C.

Diffusionless (or displacive) phase transitions allow inorganic materials to show exquisite responsiveness to external stimuli, as is illustrated vividly by the superelasticity, shape memory, and magnetocaloric effects exhibited by martensitic materials. In this Article, we present a new diffusionless transition in the compound GdCoSi 2, whose origin in frustrated bonding points toward generalizable design principles for these transformations. We first describe the synthesis of GdCoSi 2 and the determination of its structure using single crystal X-ray diffraction. While previous studies based on powder X-ray diffraction assigned this compound to the simple CeNi 1–xSi 2 structure type (space group Cmcm), ourmore » structure solution reveals a superstructure variant (space group Pbcm) in which the Co sublattice is distorted to create zigzag chains of Co atoms. DFT-calibrated Hückel calculations, coupled with a reversed approximation Molecular Orbital (raMO) analysis, trace this superstructure to the use of Co–Co isolobal bonds to complete filled 18 electron configurations on the Co atoms, in accordance with the 18–n rule. The formation of these Co–Co bonds is partially impeded, however, by a small degree of electron transfer from Si-based electronic states to those with Co–Co σ* character. The incomplete success of Co–Co bond creation suggests that these interactions are relatively weak, opening the possibility of them being overcome by thermal energy at elevated temperatures. In fact, high-temperature powder and single crystal X-ray diffraction data, as well as differential scanning calorimetry, indicate that a reversible Pbcm to Cmcm transition occurs at about 380 K. This transition is diffusionless, and the available data point toward it being first-order. We expect that similar cases of frustrated interactions could be staged in other rare earth–transition metal–main group phases, providing a potentially rich source of compounds exhibiting diffusionless transformations and the unique properties these transitions mediate.« less

X-ray electron density investigation of chemical bonding in van der Waals materials

NASA Astrophysics Data System (ADS)

Kasai, Hidetaka; Tolborg, Kasper; Sist, Mattia; Zhang, Jiawei; Hathwar, Venkatesha R.; Filsø, Mette Ø.; Cenedese, Simone; Sugimoto, Kunihisa; Overgaard, Jacob; Nishibori, Eiji; Iversen, Bo B.

2018-03-01

Van der Waals (vdW) solids have attracted great attention ever since the discovery of graphene, with the essential feature being the weak chemical bonding across the vdW gap. The nature of these weak interactions is decisive for many extraordinary properties, but it is a strong challenge for current theory to accurately model long-range electron correlations. Here we use synchrotron X-ray diffraction data to precisely determine the electron density in the archetypal vdW solid, TiS2, and compare the results with density functional theory calculations. Quantitative agreement is observed for the chemical bonding description in the covalent TiS2 slabs, but significant differences are identified for the interactions across the gap, with experiment revealing more electron deformation than theory. The present data provide an experimental benchmark for testing theoretical models of weak chemical bonding.

Crystal structure of methylprednisolone acetate form II, C 24H 32O 6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wheatley, Austin M.; Kaduk, James A.; Gindhart, Amy M.

The crystal structure of methylprednisolone acetate form II, C 24H 32O 6, has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Methylprednisolone acetate crystallizes in space groupP2 12 12 1(#19) witha= 8.17608(2),b= 9.67944(3),c= 26.35176(6) Å,V= 2085.474(6) Å 3, andZ= 4. Both hydroxyl groups act as hydrogen bond donors, resulting in a two-dimensional hydrogen bond network in theabplane. C–H…O hydrogen bonds also contribute to the crystal energy. The powder pattern is included in the Powder Diffraction File™ as entry 00-065-1412.

Insights into the mechanism of X-ray-induced disulfide-bond cleavage in lysozyme crystals based on EPR, optical absorption and X-ray diffraction studies

PubMed Central

Sutton, Kristin A.; Black, Paul J.; Mercer, Kermit R.; Garman, Elspeth F.; Owen, Robin L.; Snell, Edward H.; Bernhard, William A.

2013-01-01

Electron paramagnetic resonance (EPR) and online UV–visible absorption microspectrophotometry with X-ray crystallography have been used in a complementary manner to follow X-ray-induced disulfide-bond cleavage. Online UV–visible spectroscopy showed that upon X-irradiation, disulfide radicalization appeared to saturate at an absorbed dose of approximately 0.5–0.8 MGy, in contrast to the saturating dose of ∼0.2 MGy observed using EPR at much lower dose rates. The observations suggest that a multi-track model involving product formation owing to the interaction of two separate tracks is a valid model for radiation damage in protein crystals. The saturation levels are remarkably consistent given the widely different experimental parameters and the range of total absorbed doses studied. The results indicate that even at the lowest doses used for structural investigations disulfide bonds are already radicalized. Multi-track considerations offer the first step in a comprehensive model of radiation damage that could potentially lead to a combined computational and experimental approach to identifying when damage is likely to be present, to quantitate it and to provide the ability to recover the native unperturbed structure. PMID:24311579

Structure of semiconducting versus fast-ion conducting glasses in the Ag-Ge-Se system.

PubMed

Zeidler, Anita; Salmon, Philip S; Whittaker, Dean A J; Piarristeguy, Andrea; Pradel, Annie; Fischer, Henry E; Benmore, Chris J; Gulbiten, Ozgur

2018-01-01

The transition from a semiconductor to a fast-ion conductor with increasing silver content along the Ag x (Ge 0.25 Se 0.75 ) (100- x ) tie line (0≤ x ≤25) was investigated on multiple length scales by employing a combination of electric force microscopy, X-ray diffraction, and neutron diffraction. The microscopy results show separation into silver-rich and silver-poor phases, where the Ag-rich phase percolates at the onset of fast-ion conductivity. The method of neutron diffraction with Ag isotope substitution was applied to the x =5 and x =25 compositions, and the results indicate an evolution in structure of the Ag-rich phase with change of composition. The Ag-Se nearest-neighbours are distributed about a distance of 2.64(1) Å, and the Ag-Se coordination number increases from 2.6(3) at x =5 to 3.3(2) at x =25. For x =25, the measured Ag-Ag partial pair-distribution function gives 1.9(2) Ag-Ag nearest-neighbours at a distance of 3.02(2) Å. The results show breakage of Se-Se homopolar bonds as silver is added to the Ge 0.25 Se 0.75 base glass, and the limit of glass-formation at x ≃28 coincides with an elimination of these bonds. A model is proposed for tracking the breakage of Se-Se homopolar bonds as silver is added to the base glass.

Influence of ceramide on the internal structure and hydration of the phospholipid bilayer studied by neutron and X-ray scattering

NASA Astrophysics Data System (ADS)

Kiselev, M. A.; Zemlyanaya, E. V.; Ryabova, N. Y.; Hauss, T.; Almasy, L.; Funari, S. S.; Zbytovska, J.; Lombardo, D.

2014-07-01

Small angle neutron scattering (SANS), neutron diffraction and X-ray powder diffraction were used to investigate influence of N-stearoyl phytosphingosine (CER[NP]) and α-hydroxy- N-stearoyl phytosphingosine (CER[AP]) on the internal structure and hydration of DMPC membrane in fully and partly hydrated states at T = 30 °C. Application of Fourier analysis for diffraction data and model calculations for the SANS data evidence that addition of both CER[NP] and CER[AP] in small concentrations promotes significant changes in the organization of DMPC bilayers, such as the increase of the hydrophobic core region. SANS data evidence a decrease in the average radius and polydispersity of the vesicles that can be ascribed to hydrogen bonds interactions that favor tight lipid packing with a compact, more rigid character.

Single crystal X-ray diffraction study of the HgBa2CuO4+δ superconducting compound

NASA Astrophysics Data System (ADS)

Bordet, P.; Duc, F.; Lefloch, S.; Capponi, J. J.; Alexandre, E.; Rosa-Nunes, M.; Antipov, E. V.; Putilin, S.

1996-02-01

A high precision X-ray diffraction analysis up to sin θ/λ = 1.15 of a HgBa2CuO4+δ single crystal having a Tc of ~ 90 K is presented. The cell parameters are a = 3.8815(4), c = 9.485 (7) Å. The refinements indicate the existence of a split barium site due to the presence of excess oxygen in the mercury layer. The position of this excess oxygen might be slightly displaced from the (1/2 1/2 0) position. A 6% mercury deficiency is observed. Models, including mercury defects, substitution by copper cations, or carbonate groups, are compared. However, we obtain no definite evidence for either of the three models. A possible disorder of the Hg position, due to the formation of chemical bonds with neighbouring extra oxygen anions, could correlate to the refinements of mixed species at the Hg site. A low temperature single crystal x-ray diffraction study, and comparison of refinements for the same single crystal with different extra oxygen contents, are in progress to help clarify this problem.

Purification, crystallization and preliminary X-ray analysis of Escherichia coli UDP-N-acetylmuramoyl:L-alanine ligase (MurC).

PubMed

Deva, Taru; Pryor, KellyAnn D; Leiting, Barbara; Baker, Edward N; Smith, Clyde A

2003-08-01

UDP-N-acetylmuramoyl:L-alanine ligase (MurC) is involved in the pathway leading from UDP-N-glucosamine to the UDP-N-acetylmuramoyl:pentapeptide unit, which is the building block for the peptidoglycan layer found in all bacterial cell walls. The pathways leading to the biosynthesis of the peptidoglycan layer are important targets for the development of novel antibiotics, since animal cells do not contain these pathways. MurC is the first of four similar ATP-dependent amide-bond ligases which share primary and tertiary structural similarities. The crystal structures of three of these have been determined by X-ray crystallography, giving insights into the binding of the carbohydrate substrate and the ATP. Diffraction-quality crystals of the enzyme MurC have been obtained in both native and selenomethionine forms and X-ray diffraction data have been collected at the Se edge at a synchrotron source. The crystals are orthorhombic, with unit-cell parameters a = 73.9, b = 93.6, c = 176.8 A, and diffraction has been observed to 2.6 A resolution.

Structural properties of a family of hydrogen-bonded co-crystals formed between gemfibrozil and hydroxy derivatives of t-butylamine, determined directly from powder X-ray diffraction data

NASA Astrophysics Data System (ADS)

Cheung, Eugene Y.; David, Sarah E.; Harris, Kenneth D. M.; Conway, Barbara R.; Timmins, Peter

2007-03-01

We report the formation and structural properties of co-crystals containing gemfibrozil and hydroxy derivatives of t-butylamine H 2NC(CH 3) 3-n(CH 2OH) n, with n=0, 1, 2 and 3. In each case, a 1:1 co-crystal is formed, with transfer of a proton from the carboxylic acid group of gemfibrozil to the amino group of the t-butylamine derivative. All of the co-crystal materials prepared are polycrystalline powders, and do not contain single crystals of suitable size and/or quality for single crystal X-ray diffraction studies. Structure determination of these materials has been carried out directly from powder X-ray diffraction data, using the direct-space Genetic Algorithm technique for structure solution followed by Rietveld refinement. The structural chemistry of this series of co-crystal materials reveals well-defined structural trends within the first three members of the family ( n=0, 1, 2), but significantly contrasting structural properties for the member with n=3.

Raman scattering and X-ray powder diffraction studies of hydrate layered perovskites: dirubidium aquapentafluoromanganate(III) and dipotassium aquapentafluoroferrate(III)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galicka, Karolina; Slodczyk, Aneta; Ratuszna, Alicja

2004-06-08

The structural and vibrational properties of above mentioned crystals were determined using X-ray powder diffraction and Raman scattering experiments. At room temperature hydrate layered perovskites: Rb{sub 2}MnF{sub 5}{center_dot}H{sub 2}O and K{sub 2}FeF{sub 5}{center_dot}H{sub 2}O exhibit orthorhombic--Cmcm (D{sub 2h}{sup 17}) and monoclinic--C2/c (C{sub 2h}{sup 6}) symmetry. Their structure is built up of MnF{sub 6} or FeF{sub 5}{center_dot}H{sub 2}O octahedra forming trans-linked zig-zag chains or hydrogen bonded zig-zag chains along the major crystallographic direction [0 0 1], respectively. To confirm crystal structures and to describe lattice dynamics of these compounds the vibrational normal modes (in {gamma} point of first Brillouin zone) weremore » calculated on the base of the group theory analysis and compared with the spectra obtained from Raman scattering experiments. A relatively good reliability was obtained for both X-ray powder diffraction and Raman scattering.« less

Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Popa, Karin; Raison, Philippe E., E-mail: philippe.raison@ec.europa.eu; Martel, Laura

2015-10-15

PuPO{sub 4} was prepared by a solid state reaction method and its crystal structure at room temperature was solved by powder X-ray diffraction combined with Rietveld refinement. High resolution XANES measurements confirm the +III valence state of plutonium, in agreement with valence bond derivation. The presence of the americium (as β{sup −} decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state {sup 31}P NMR agrees with the XANES results and the presence of a solid-solution. - Graphical abstract: A full structural analysis of PuPO{sub 4} based on Rietveld analysis ofmore » room temperature X-ray diffraction data, XANES and MAS NMR measurements was performed. - Highlights: • The crystal structure of PuPO{sub 4} monazite is solved. • In PuPO{sub 4} plutonium is strictly trivalent. • The presence of a minute amount of Am{sup III} is highlighted. • We propose PuPO{sub 4} as a potential reference material for spectroscopic and microscopic studies.« less

Physicochemical behavior of several kinds of paper under gamma irradiation

NASA Astrophysics Data System (ADS)

Jiménez-Reyes, Melania; Tenorio, Dolores; Rojas-Robles, Mariela; García-Rosales, Genoveva

2018-07-01

Several kinds of paper (Bond, Amate, Rice, Press, and Whatman#1) were studied in their original condition and were then exposed to gamma radiation between 3 and 15 kGy (0.9 kGy/h) with intervals of 3 kGy. The length and width of fibers (SEM) as well as pH were measured, and the chemical composition was determined by EDS. Pyrolysis characteristics (TGA and DTC), transmittance spectra by IR and X-ray diffraction patterns were studied as well. Whatman#1 contains only cellulose; whereas Bond, Press and Rice papers also contain calcite and Amate whewellite. All X-ray diffraction patterns showed Type I semicrystalline cellulose, but a slight presence of Type II was noted in the artisan papers (Amate and Rice). These results were confirmed by IR spectra and thermogravimetric analyses. Due to gamma irradiation no acidification nor change of fiber sizes or alteration of other studied parameters were observed. Therefore, these conditions may be recommended for the treatment of some deteriorated documents.

Trinuclear organooxotin assemblies from solvothermal synthesis reaction: Crystal structure, hydrogen bonding and π π stacking interaction

NASA Astrophysics Data System (ADS)

Ma, Chunlin; Sun, Junshan; Zhang, Rufen

2007-05-01

Two new trinuclear mono-organooxotin(IV) complexes with 2,3,4,5-tetrafluorobenzoic acid and sodium perchlorate of the types: [(SnR) 3(OH)(2,3,4,5-F 4C 6HCO 2) 4 · ClO 4] · [O 2CC 6HF 4](R = PhCH 2, 1; o- F-PhCH 2 for 2), have been solvothermally synthesized and structurally characterized by elemental, IR, 1H, 13C and 119Sn NMR and X-ray crystallography diffraction analyses. Complex 2 is also characterized by X-ray crystallography diffraction analyses. In complex 2, four carboxyl groups and a perchlorate bridged three tin atoms in a cyclohexane chair arrangement and form the basic framework. A hydroxyl group comprises the oxygen components of the stannoxane ring system. In these complexes, weak but significant intramolecular hydrogen bonding and π-π stacking interaction are also shown. These contacts lead to aggregation and supramolecular assembly of complexes 1 and 2 into 1D or 2D framework.

Synthesis and spectral studies on Cd(II) dithiocarbamate complexes and their use as precursors for CdS nanoparticles

NASA Astrophysics Data System (ADS)

Sathiyaraj, Ethiraj; Padmavathy, Krishnaraj; Kumar, Chandran Udhaya; Krishnan, Kannan Gokula; Ramalingan, Chennan

2017-11-01

Bis(N-cyclopropyl-N-4-chlorobenzyldithiocarbamato-S,S‧)cadmium(II) (1) and (2,2‧-bipyridine) bis(N-cyclopropyl-N-4-chlorobenzyldithiocarbamato-S,S‧)cadmium(II) (2) have been synthesized and characterized by FT-IR, 1HNMR and 13C NMR analyses. For the complex 2, single crystal X-ray diffraction analysis and computational studies (optimized geometry, HOMO-LUMO and MEP) have been executed employing DFT/B3LYP method with LANL 2DZ basic set. The optimized bond lengths and bond angles agree well with the experimental results. The complexes 1 and 2 have been used as single source precursors for the synthesis of ethyleneglycol capped CdS1 and CdS2 nanoparticles, respectively. CdS1 and CdS2 nanoparticles have been synthesized by solvothermal method. PXRD, SEM, Elemental colour mapping, EDAX, TEM and UV-Vis spectroscopy have been used to characterize the as-prepared CdS nanoparticles. The X-ray diffraction pattern confirms both their hexagonal structures.

Electronic Structure and Bonding in Complex Biomolecule

NASA Astrophysics Data System (ADS)

Ouyang, Lizhi

2005-03-01

For over a century vitamin B12 and its enzyme cofactor derivates have persistently attracted research efforts for their vital biological role, unique Co-C bonding, rich red-ox chemistry, and recently their candidacies as drug delivery vehicles etc. However, our understanding of this complex metalorganic molecule's efficient enzyme activated catalytic power is still controversial. We have for the first time calculated the electronic structure, Mulliken effective charge and bonding of a whole Vitamin B12 molecule without any structural simplification by first- principles approaches based on density functional theory using structures determined by high resolution X-ray diffraction. A partial density of states analysis shows excellent agreement with X-ray absorption data and has been used successfully to interpret measured optical absorption spectra. Mulliken bonding analysis of B12 and its derivatives reveal noticeable correlations between the two axial ligands which could be exploited by the enzyme to control the catalytic process. Our calculated X-ray near edge structure of B12 and its derivates using Slater's transition state theory are also in good agreement with experiments. The same approach has been applied to other B12 derivatives, ferrocene peptides, and recently DNA molecules.

Immobilization of Chlorosulfonyl-Calix[4]arene onto the surface of silica gel through the directly estrification

NASA Astrophysics Data System (ADS)

Taghvaei-Ganjali, Saeed; Zadmard, Reza; Saber-Tehrani, Mandana

2012-06-01

For the first time Chlorosulfonyl-Calix[4]arene has been chemically bonded to silica gel through the directly estrification without silane coupling agent to prepare Chlorosulfonyl-Calix[4]arene-bonded silica gel. Sample characterization was performed by various techniques such as elemental analysis, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), powder X-ray diffraction (XRD), N2 adsorption-desorption, thermal gravimetric analysis (TGA), 29Si CP/MAS spectroscopy and acid-base titration. All data approve the successful incorporation of organic group via covalent bond. From the comparison between sulfur content determined by elemental analysis and the number of H+ determined by acid-base titration, it was shown that two ester units took place onto the new synthesized sample and two acidic sites exist on the surface.

Bonding in uranium(V) hexafluoride based on the experimental electron density distribution measured at 20 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gianopoulos, Christopher G.; Zhurov, Vladimir V.; Minasian, Stefan G.

The electron density distribution of [PPh 4][UF 6] was obtained from high-resolution X-ray diffraction data measured at 20 K. The electron density was modeled with an augmented Hansen–Coppens multipolar formalism. Topological analysis reveals that the U–F bond is of incipient covalent nature. Theoretical calculations add further support to the bonding description gleaned from the experimental model. The impact of the uranium anomalous dispersion terms on the refinement is also discussed.

Bonding in uranium(V) hexafluoride based on the experimental electron density distribution measured at 20 K

DOE PAGES

Gianopoulos, Christopher G.; Zhurov, Vladimir V.; Minasian, Stefan G.; ...

2017-02-06

The electron density distribution of [PPh 4][UF 6] was obtained from high-resolution X-ray diffraction data measured at 20 K. The electron density was modeled with an augmented Hansen–Coppens multipolar formalism. Topological analysis reveals that the U–F bond is of incipient covalent nature. Theoretical calculations add further support to the bonding description gleaned from the experimental model. The impact of the uranium anomalous dispersion terms on the refinement is also discussed.

Use of a miniature diamond-anvil cell in high-pressure single-crystal neutron Laue diffraction

PubMed Central

Binns, Jack; Kamenev, Konstantin V.; McIntyre, Garry J.; Moggach, Stephen A.; Parsons, Simon

2016-01-01

The first high-pressure neutron diffraction study in a miniature diamond-anvil cell of a single crystal of size typical for X-ray diffraction is reported. This is made possible by modern Laue diffraction using a large solid-angle image-plate detector. An unexpected finding is that even reflections whose diffracted beams pass through the cell body are reliably observed, albeit with some attenuation. The cell body does limit the range of usable incident angles, but the crystallographic completeness for a high-symmetry unit cell is only slightly less than for a data collection without the cell. Data collections for two sizes of hexamine single crystals, with and without the pressure cell, and at 300 and 150 K, show that sample size and temperature are the most important factors that influence data quality. Despite the smaller crystal size and dominant parasitic scattering from the diamond-anvil cell, the data collected allow a full anisotropic refinement of hexamine with bond lengths and angles that agree with literature data within experimental error. This technique is shown to be suitable for low-symmetry crystals, and in these cases the transmission of diffracted beams through the cell body results in much higher completeness values than are possible with X-rays. The way is now open for joint X-ray and neutron studies on the same sample under identical conditions. PMID:27158503

Chemical bonding in TiSb(2) and VSb(2): a quantum chemical and experimental study.

PubMed

Armbrüster, Marc; Schnelle, Walter; Schwarz, Ulrich; Grin, Yuri

2007-08-06

The chemical bonding in the isostructural intermetallic compounds TiSb2 and VSb2, crystallizing in the CuAl2 type, was investigated by means of quantum chemical calculations, particularly the electron localization function (ELF), as well as by Raman spectroscopy, Hall effect and conductivity measurements on oriented single crystals, and high-pressure X-ray powder diffraction. The homogeneity ranges of the compounds were determined by powder X-ray diffraction, WDXS, and DSC measurements. TiSb2 exhibits no significant homogeneity range, while VSb2 shows a small homogeneity range of approximately 0.3 at. %. According to the ELF calculations, the Sb atoms form dumbbells via a two-center two-electron bond, while the T atoms (T = Ti, V) build up chains along the crystallographic c-axis. Both building units are connected by covalent T-Sb-T three-center bonds, thus forming a three-dimensional network. The strength of the bonds involving Sb was determined by fitting a force constant model to the vibrational mode frequencies observed by polarized Raman measurements on oriented single crystals. The resulting bond order of the Sb2 dumbbells is 1, while the strength of the three-center bonds resembles a bond order of 1.5. The weak pressure dependence of the c/a ratio confirms the slightly different bonding picture in TiSb2 compared to that in CuAl2. Electrical transport measurements show the presence of free charge carriers, as well as a metal-like temperature dependence of the electrical resistivity.

Structural characterization and aging of glassy pharmaceuticals made using acoustic levitation.

PubMed

Benmore, Chris J; Weber, J K R; Tailor, Amit N; Cherry, Brian R; Yarger, Jeffery L; Mou, Qiushi; Weber, Warner; Neuefeind, Joerg; Byrn, Stephen R

2013-04-01

Here, we report the structural characterization of several amorphous drugs made using the method of quenching molten droplets suspended in an acoustic levitator. (13) C NMR, X-ray, and neutron diffraction results are discussed for glassy cinnarizine, carbamazepine, miconazole nitrate, probucol, and clotrimazole. The (13) C NMR results did not find any change in chemical bonding induced by the amorphization process. High-energy X-ray diffraction results were used to characterize the ratio of crystalline to amorphous material present in the glasses over a period of 8 months. All the glasses were stable for at least 6 months except carbamazepine, which has a strong tendency to crystallize within a few months. Neutron and X-ray pair distribution function analyses were applied to the glassy materials, and the results were compared with their crystalline counterparts. The two diffraction techniques yielded similar results in most cases and identified distinct intramolecular and intermolecular correlations. The intramolecular scattering was calculated based on the crystal structure and fit to the measured X-ray structure factor. The resulting intermolecular pair distribution functions revealed broad-nearest and next-nearest neighbor molecule-molecule correlations. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 102:1290-1300, 2013. Copyright © 2013 Wiley Periodicals, Inc.

Synthesis of PbS/TiO2 nanocomposite materials using the sol-gel process via the incorporation of lead thiolates

NASA Astrophysics Data System (ADS)

Patel, Khushikumari

PbS/TiO2 nanocomposites were prepared by two methods using the sol-gel process: a one step process and a multi-step process. The incorporation of 3-mercaptopropionic acid, followed by the addition of Pb2+ generated covalently incorporated lead thiolate precursors which can then be converted to PbS/TiO2 nanocomposites by controlled thermal decomposition. Various ratios of bifunctional linker to matrix were used to monitor the incorporation of functional groups of the ceramic matrix, and the sol-gel process was used to produce a high yield ceramic materials. This allows solutions to chemically bind and form solid state ceramics, while allowing complex compounds to combine with a high degree of homogeneity. 3-mercaptoproprionic acid, was added to the titania gel, and as a source of sulfur component to bind to the titania. PbS/TiO2 nanocomposites were studied using FTIR spectroscopy. The covalent bonding between PbS and the titania ceramics was also confirmed with the signal intensity in the infrared spectra. The success of the covalent bond between the thiolate and ceramics led to possibility of nanocomposites. X-ray diffraction was used analyze the structure of the nanocomposites X-ray diffraction results showed lead sulfide nanocrystals in the ceramic matrix as well as the size of the particles. The presence of crystalline PbS and particle size was determined using powder X-ray diffraction.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yin, Fei; Chen, Jing; Liang, Yongfeng

Two coordination polymers [Co(dnbab){sub 2}(bimb)](H{sub 2}O){sub 4} (1) and [Zn(dnbab){sub 2}(bimb)](H{sub 2}O){sub 5} (2) (Hdnbab=4-[(3,5-dinitrobenzoyl)amino]benzoic acid, bimb=1,4-bis(1-imidazolyl) benzene) have been solvothermally synthesized. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by powder X-ray diffraction (PXRD) and thermogravimetric (TG) analyses. Complexes 1 and 2 are isostructures and each displays an one-dimensional (1D) zigzag chain, which further forms a 3D supramolecular architecture with 1-D channels via inter-chain π–π interactions and hydrogen bonds. Moreover, the magnetic properties of 1 and fluorescent properties of 2 have been investigated. - Graphical abstract: Two coordination supramolecular frameworks [Co(dnbab){sub 2}(bimb)](H{sub 2}O){sub 4}(1)more » and [Zn(dnbab){sub 2}(bimb)](H{sub 2}O){sub 5}(2) (Hdnbab=4-[(3,5-dinitrobenzoyl)amino]benzoic acid, bimb=1,4-bis(1-imidazolyl) benzene) have been synthesized and characterized by X-ray single-crystal diffraction. Their thermal, magnetic and fluorescent properties have also been studied. - Highlights: • Two isomorphic Co(II)/Zn(II) complexes with the mixed-ligands have been synthesized. • Hydrogen bonds and π–π stacking interactions directed the final 3-D architecture assembly. • Both Co(II) and Zn(II) complexes show good thermal stability. • Co complex exhibits antiferromagnetic interaction. • The fluorescent property of Zn(II) complex has been investigated in the solid state.« less

Ultrafast molecular processes mapped by femtosecond x-ray diffraction

NASA Astrophysics Data System (ADS)

Elsaesser, Thomas

2012-02-01

X-ray diffraction with a femtosecond time resolution allows for mapping photoinduced structural dynamics on the length scale of a chemical bond and in the time domain of atomic and molecular motion. In a pump-probe approach, a femtosecond excitation pulse induces structural changes which are probed by diffracting a femtosecond hard x-ray pulse from the excited sample. The transient angular positions and intensities of diffraction peaks give insight into the momentary atomic or molecular positions and into the distribution of electronic charge density. The simultaneous measurement of changes on different diffraction peaks is essential for determining atom positions and charge density maps with high accuracy. Recent progress in the generation of ultrashort hard x-ray pulses (Cu Kα, wavelength λ=0.154 nm) in laser-driven plasma sources has led to the implementation of the powder diffraction and the rotating crystal method with a time resolution of 100 fs. In this contribution, we report new results from powder diffraction studies of molecular materials. A first series of experiments gives evidence of a so far unknown concerted transfer of electrons and protons in ammonium sulfate [(NH4)2SO4], a centrosymmetric structure. Charge transfer from the sulfate groups results in the sub-100 fs generation of a confined electron channel along the c-axis of the unit cell which is stabilized by transferring protons from the adjacent ammonium groups into the channel. Time-dependent charge density maps display a periodic modulation of the channel's charge density by low-frequency lattice motions with a concerted electron and proton motion between the channel and the initial proton binding site. A second study addresses atomic rearrangements and charge dislocations in the non-centrosymmetric potassium dihydrogen phosphate [KH2PO4, KDP]. Photoexcitation generates coherent low-frequency motions along the LO and TO phonon coordinates, leaving the average atomic positions unchanged. The time-dependent maps of electron density demonstrate a concomitant oscillatory relocation of electronic charge with a spatial amplitude of the order of a chemical bond length, two orders of magnitude larger than the vibrational amplitudes. The coherent phonon motions drive the charge relocation, similar to a soft mode driven phase transition between the ferro- and paraelectric phase of KDP.

Hydrogen bonded nonlinear optical γ-glycine: Crystal growth and characterization

NASA Astrophysics Data System (ADS)

Narayana Moolya, B.; Jayarama, A.; Sureshkumar, M. R.; Dharmaprakash, S. M.

2005-07-01

Single crystals of γ-glycine(GG) were grown by solvent evaporation technique from a mixture of aqueous solutions of glycine and ammonium nitrate at ambient temperature. X-ray diffraction, thermogravimetric/differential thermal analysis, Fourier transform infrared spectral techniques were employed to characterize the crystal. The lattice parameters were calculated and they agree well with the reported values. GG exists as dipolar ions in which the carboxyl group is present as a carboxylate ion and the amino group as an ammonium ion. Due to this dipolar nature, glycine has a high decomposition temperature. The UV cutoff of GG is below 300 nm and has a wide transparency window, which is suitable for second harmonic generation of laser in the blue region. Nonlinear optical characteristics of GG were studied using Q switched Nd:YAG laser ( λ=1064 nm). The second harmonic generation conversion efficiency of GG is 1.5 times that of potassium dihydrogen phosphate . The X-ray diffraction and Fourier transform infrared spectral studies show the presence of strong hydrogen bonds which create and stabilize the crystal structure in GG. The main contributions to the nonlinear optical properties in GG results from the presence of the hydrogen bond and from the vibrational part due to very intense infrared bands of the hydrogen bond vibrations. GG is thermally stable up to 441 K.

The subtle balance of weak supramolecular interactions: The hierarchy of halogen and hydrogen bonds in haloanilinium and halopyridinium salts.

PubMed

Raatikainen, Kari; Cametti, Massimo; Rissanen, Kari

2010-01-15

THE SERIES OF HALOANILINIUM AND HALOPYRIDINIUM SALTS: 4-IPhNH₃Cl (1), 4-IPhNH₃Br (5), 4-IPhNH₃H₂PO₄ (6), 4-ClPhNH₃H₂PO₄ (8), 3-IPyBnCl (9), 3-IPyHCl (10) and 3-IPyH-5NIPA (3-iodopyridinium 5-nitroisophthalate, 13), where hydrogen or/and halogen bonding represents the most relevant non-covalent interactions, has been prepared and characterized by single crystal X-ray diffraction. This series was further complemented by extracting some relevant crystal structures: 4-BrPhNH₃Cl (2, CCDC ref. code TAWRAL), 4-ClPhNH₃Cl (3, CURGOL), 4-FPhNH₃Cl (4, ANLCLA), 4-BrPhNH₃H₂PO₄, (7, UGISEI), 3-BrPyHCl, (11, CIHBAX) and 3-ClPyHCl, (12, VOQMUJ) from Cambridge Structural Database for sake of comparison. Based on the X-ray data it was possible to highlight the balance between non-covalent forces acting in these systems, where the relative strength of the halogen bonding C-X...A⁻ (X = I, Br or Cl) and the ratio between the halogen and hydrogen bonds [C-X...A⁻ : D-H...A⁻] varied across the series.

A Novel Coordination Polymer Based on Trinuclear Cobalt Building Blocks Cluster: Synthesis, Crystal Structure, and Properties

NASA Astrophysics Data System (ADS)

Lu, J. F.; Tang, Z. H.; Shi, J.; Ge, H. G.; Jiang, M.; Song, J.; Jin, L. X.

2017-12-01

The title compound {[Co3(μ3-OH)(μ2-H2O)2(H2O)5(BTC)2] · 6H2O} n (H3BTC is a 1,3,5-benzenetricarboxylic acid) was prepared and characterized by single crystal and powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric and elemental analyses. The single crystal X-ray diffraction reveals that the title compound consists of 1D infinite zigzag chains which were constructed by trinuclear cobalt cluster and BTC3- ligand. Neighbouring above-mentioned 1D infinite zigzag chains are further linked by intermolecular hydrogen bonding to form a 3D supermolecular structure. In addition, the luminescent properties of the title compound were investigated.

The use of neutron scattering to determine the functional structure of glycoside hydrolase.

PubMed

Nakamura, Akihiko; Ishida, Takuya; Samejima, Masahiro; Igarashi, Kiyohiko

2016-10-01

Neutron diffraction provides different information from X-ray diffraction, because neutrons are scattered by atomic nuclei, whereas X-rays are scattered by electrons. One of the key advantages of neutron crystallography is the ability to visualize hydrogen and deuterium atoms, making it possible to observe the protonation state of amino acid residues, hydrogen bonds, networks of water molecules and proton relay pathways in enzymes. But, because of technical difficulties, less than 100 enzyme structures have been evaluated by neutron crystallography to date. In this review, we discuss the advantages and disadvantages of neutron crystallography as a tool to investigate the functional structure of glycoside hydrolases, with some examples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Evidence of monotropic hexatic tilted smectic phase in the phase sequence of ferroelectric liquid crystal

NASA Astrophysics Data System (ADS)

Różycka, Anna; Deptuch, Aleksandra; Jaworska-Gołąb, Teresa; Węgłowska, Dorota; Marzec, Monika

2018-02-01

Physical properties of a new ferroelectric liquid crystal have been studied by complementary methods: differential scanning calorimetry, polarizing optical microscopy, dielectric and X-ray diffraction. It was found that next to enantiotropic ferroelectric smectic C* phase, the monotropic smectic phase appears at cooling. X-ray diffraction measurements allowed to identify this phase as hexatic tilted smectic. Temperature dependence of spontaneous polarization, tilt angle of molecules and switching time were found in both liquid crystalline phases at cooling. Based on the dielectric results, the dielectric processes were identified as Goldstone mode in the smectic C* phase, whereas as the bond-orientation-like phason and the bulk domain mode in the monotropic hexatic tilted smectic phase.

Chemical complexity induced local structural distortion in NiCoFeMnCr high-entropy alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fuxiang; Tong, Yang; Jin, Ke

In order to study chemical complexity-induced lattice distortion in high-entropy alloys, the static Debye–Waller (D-W) factor of NiCoFeMnCr solid solution alloy is measured with low temperature neutron diffraction, ambient X-ray diffraction, and total scattering methods. Here, the static atomic displacement parameter of the multi-element component alloy at 0 K is 0.035–0.041 Å, which is obvious larger than that of element Ni (~0 Å). The atomic pair distance between individual atoms in the alloy investigated with extended X-ray absorption fine structure (EXAFS) measurements indicates that Mn has a slightly larger bond distance (~0.4%) with neighbor atoms than that of others.

Chemical complexity induced local structural distortion in NiCoFeMnCr high-entropy alloy

DOE PAGES

Zhang, Fuxiang; Tong, Yang; Jin, Ke; ...

2018-06-16

In order to study chemical complexity-induced lattice distortion in high-entropy alloys, the static Debye–Waller (D-W) factor of NiCoFeMnCr solid solution alloy is measured with low temperature neutron diffraction, ambient X-ray diffraction, and total scattering methods. Here, the static atomic displacement parameter of the multi-element component alloy at 0 K is 0.035–0.041 Å, which is obvious larger than that of element Ni (~0 Å). The atomic pair distance between individual atoms in the alloy investigated with extended X-ray absorption fine structure (EXAFS) measurements indicates that Mn has a slightly larger bond distance (~0.4%) with neighbor atoms than that of others.

Analysis of the Photomagnetic Properties of Cyano-Bridged Heterobimetallic Complexes by X-Ray Diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Svendsen, Helle; Jørgensen, Mads Ry Vogel; Overgaard, Jacob

2012-10-11

Single crystal synchrotron X-ray diffraction measurements have been carried out on [Nd(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O (DMF = dimethyl-formamide), 1; [Y(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 2; [Ce(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 3; [Sm(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 4; [Tb(DMF){sub 4}(H{sub 2}O)3({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 5; [Yb(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 6; and [Nd(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Co(CN){sub 5}] {center_dot} H{sub 2}O, 7, at 15(2) K with and without UV illumination of the crystals. Significant changes in unit cell parameters are observed for all of themore » iron-containing complexes, while compound 7 shows no response to UV illumination. These results are consistent with previous results and are furthermore reproduced by powder synchrotron X-ray diffraction for compounds 1 and 7. Photoexcited crystal structures have been determined for 1-6 from refinements of two-conformer models, and excited state occupancies in the range 80-94% are found. Significant bond length changes are observed for the Fe-ligand bonds (up to 0.06 {angstrom}), the cyano bonds (up to 0.02 {angstrom}), and the lanthanide-ligand bonds (up to 0.1 {angstrom}). On the contrary, powder X-ray diffraction on the simple compound K{sub 3}Fe(CN)6, 8, upon UV illumination does not show any structural changes, suggesting that the photomagnetic effect requires the presence of both the transition metal and the lanthanide ion. Photomagnetic measurements show an increase in magnetization of the excited state of 1 of up to 3%, which is much diminished compared with previously published values of 45%. Furthermore, they show that the isostructural complex [La(DMF){sub 4}(H{sub 2}O){sub 3}({mu}-CN)Fe(CN){sub 5}] {center_dot} H{sub 2}O, 9, exhibits identical magnetic responses in the UV-induced excited crystal structure.« less

Compressibility of Cs2SnBr6 by X-ray diffraction and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Yuan, Guan; Huang, Shengxuan; Niu, Jingjing; Qin, Shan; Wu, Xiang; Ding, Hongrui; Lu, Anhuai

2018-07-01

Cs2SnBr6, one promising material applied in perovskite solar cells, has been investigated up to 20 GPa by synchrotron X-ray diffraction and Raman spectroscopy. Both experimental data demonstrate that no phase transition occurs up to 20 GPa. By fitting the third-order Birch-Murnaghan equation of state, we have obtained V0 = 1288 (14) Å3, K0 = 11 (1) GPa and K0‧ = 7 (1). The ultralow value of bulk modulus K0 demonstrates the soft nature of Cs2SnBr6. Combining calculated values with experimental results, we find that x coordinate of Sn (x,0,0) atoms increases and Snsbnd Br bond lengths get shortened on compression. We have assigned vibrational peaks of Cs2SnBr6 in Raman measurements, and all the three Raman bands present nonlinear correlations with pressure.

White-Beam X-ray Diffraction and Radiography Studies on High-Boron Containing Borosilicate Glass at High Pressures

NASA Astrophysics Data System (ADS)

Ham, Kathryn; Vohra, Yogesh; Kono, Yoshio; Wereszczak, Andrew; Patel, Parimal

Multi-angle energy-dispersive x-ray diffraction studies and white-beam x-ray radiography were conducted with a cylindrically shaped (1 mm diameter and 0.7 mm high) high-boron content borosilicate glass sample (17.6% B2O3) to a pressure of 13.7 GPa using a Paris-Edinburgh (PE) press at Beamline 16-BM-B, HPCAT of the Advanced Photon Source. The measured structure factor S(q) to large q = 19 Å-1, is used to determine information about the internuclear bond distances between various species of atoms within the glass sample. Sample pressure was determined with gold as a pressure standard. The sample height as measured by radiography showed an overall uniaxial compression of 22.5 % at 13.7 GPa with 10.6% permanent compaction after decompression to ambient conditions. The reduced pair distribution function G(r) was extracted and Si-O, O-O, and Si-Si bond distances were measured as a function of pressure. Raman spectroscopy of pressure recovered sample as compared to starting material showed blue-shift and changes in intensity and widths of Raman bands associated with silicate and B3O6 boroxol rings. US Army Research Office under Grant No. W911NF-15-1-0614.

Structure of semiconducting versus fast-ion conducting glasses in the Ag–Ge–Se system

PubMed Central

2018-01-01

The transition from a semiconductor to a fast-ion conductor with increasing silver content along the Agx(Ge0.25Se0.75)(100−x) tie line (0≤x≤25) was investigated on multiple length scales by employing a combination of electric force microscopy, X-ray diffraction, and neutron diffraction. The microscopy results show separation into silver-rich and silver-poor phases, where the Ag-rich phase percolates at the onset of fast-ion conductivity. The method of neutron diffraction with Ag isotope substitution was applied to the x=5 and x=25 compositions, and the results indicate an evolution in structure of the Ag-rich phase with change of composition. The Ag–Se nearest-neighbours are distributed about a distance of 2.64(1) Å, and the Ag–Se coordination number increases from 2.6(3) at x=5 to 3.3(2) at x=25. For x=25, the measured Ag–Ag partial pair-distribution function gives 1.9(2) Ag–Ag nearest-neighbours at a distance of 3.02(2) Å. The results show breakage of Se–Se homopolar bonds as silver is added to the Ge0.25Se0.75 base glass, and the limit of glass-formation at x≃28 coincides with an elimination of these bonds. A model is proposed for tracking the breakage of Se–Se homopolar bonds as silver is added to the base glass. PMID:29410843

Anisotropic pyrochemical microetching of poly(tetrafluoroethylene) initiated by synchrotron radiation-induced scission of molecule bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamaguchi, Akinobu, E-mail: yamaguti@lasti.u-hyogo.ac.jp, E-mail: utsumi@lasti.u-hyogo.ac.jp; Kido, Hideki; Utsumi, Yuichi, E-mail: yamaguti@lasti.u-hyogo.ac.jp, E-mail: utsumi@lasti.u-hyogo.ac.jp

2016-02-01

We developed a process for micromachining polytetrafluoroethylene (PTFE): anisotropic pyrochemical microetching induced by synchrotron X-ray irradiation. X-ray irradiation was performed at room temperature. Upon heating, the irradiated PTFE substrates exhibited high-precision features. Both the X-ray diffraction peak and Raman signal from the irradiated areas of the substrate decreased with increasing irradiation dose. The etching mechanism is speculated as follows: X-ray irradiation caused chain scission, which decreased the number-average degree of polymerization. The melting temperature of irradiated PTFE decreased as the polymer chain length decreased, enabling the treated regions to melt at a lower temperature. The anisotropic pyrochemical etching process enabledmore » the fabrication of PTFE microstructures with higher precision than simultaneously heating and irradiating the sample.« less

High-pressure studies with x-rays using diamond anvil cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Guoyin; Mao, Ho Kwang

2016-11-22

Pressure profoundly alters all states of matter. The symbiotic development of ultrahigh-pressure diamond anvil cells, to compress samples to sustainable multi-megabar pressures; and synchrotron x-ray techniques, to probe materials' properties in situ, has enabled the exploration of rich high-pressure (HP) science. In this article, we first introduce the essential concept of diamond anvil cell technology, together with recent developments and its integration with other extreme environments. We then provide an overview of the latest developments in HP synchrotron techniques, their applications, and current problems, followed by a discussion of HP scientific studies using x-rays in the key multidisciplinary fields. Thesemore » HP studies include: HP x-ray emission spectroscopy, which provides information on the filled electronic states of HP samples; HP x-ray Raman spectroscopy, which probes the HP chemical bonding changes of light elements; HP electronic inelastic x-ray scattering spectroscopy, which accesses high energy electronic phenomena, including electronic band structure, Fermi surface, excitons, plasmons, and their dispersions; HP resonant inelastic x-ray scattering spectroscopy, which probes shallow core excitations, multiplet structures, and spin-resolved electronic structure; HP nuclear resonant x-ray spectroscopy, which provides phonon densities of state and time-resolved Mössbauer information; HP x-ray imaging, which provides information on hierarchical structures, dynamic processes, and internal strains; HP x-ray diffraction, which determines the fundamental structures and densities of single-crystal, polycrystalline, nanocrystalline, and non-crystalline materials; and HP radial x-ray diffraction, which yields deviatoric, elastic and rheological information. Integrating these tools with hydrostatic or uniaxial pressure media, laser and resistive heating, and cryogenic cooling, has enabled investigations of the structural, vibrational, electronic, and magnetic properties of materials over a wide range of pressure-temperature conditions.« less

High-pressure studies with x-rays using diamond anvil cells

NASA Astrophysics Data System (ADS)

Shen, Guoyin; Mao, Ho Kwang

2017-01-01

Pressure profoundly alters all states of matter. The symbiotic development of ultrahigh-pressure diamond anvil cells, to compress samples to sustainable multi-megabar pressures; and synchrotron x-ray techniques, to probe materials’ properties in situ, has enabled the exploration of rich high-pressure (HP) science. In this article, we first introduce the essential concept of diamond anvil cell technology, together with recent developments and its integration with other extreme environments. We then provide an overview of the latest developments in HP synchrotron techniques, their applications, and current problems, followed by a discussion of HP scientific studies using x-rays in the key multidisciplinary fields. These HP studies include: HP x-ray emission spectroscopy, which provides information on the filled electronic states of HP samples; HP x-ray Raman spectroscopy, which probes the HP chemical bonding changes of light elements; HP electronic inelastic x-ray scattering spectroscopy, which accesses high energy electronic phenomena, including electronic band structure, Fermi surface, excitons, plasmons, and their dispersions; HP resonant inelastic x-ray scattering spectroscopy, which probes shallow core excitations, multiplet structures, and spin-resolved electronic structure; HP nuclear resonant x-ray spectroscopy, which provides phonon densities of state and time-resolved Mössbauer information; HP x-ray imaging, which provides information on hierarchical structures, dynamic processes, and internal strains; HP x-ray diffraction, which determines the fundamental structures and densities of single-crystal, polycrystalline, nanocrystalline, and non-crystalline materials; and HP radial x-ray diffraction, which yields deviatoric, elastic and rheological information. Integrating these tools with hydrostatic or uniaxial pressure media, laser and resistive heating, and cryogenic cooling, has enabled investigations of the structural, vibrational, electronic, and magnetic properties of materials over a wide range of pressure-temperature conditions.

Crystal structure of hydrocortisone acetate, C23H32O6

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaduk, James A.; Gindhart, Amy M.; Blanton, Thomas N.

The crystal structure of hydrocortisone acetate has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Hydrocortisone acetate crystallizes in space groupP2 1(#4) witha= 8.85173(3) Å,b= 13.53859(3) Å,c= 8.86980(4) Å,β= 101.5438(3)°,V= 1041.455(6) Å 3, andZ= 2. Both hydroxyl groups form hydrogen bonds to the ketone oxygen atom on the steroid ring system, resulting in a three-dimensional hydrogen bond network. The powder pattern has been submitted to ICDD for inclusion in the Powder Diffraction File™.

The Crystal Structures of Potentially Tautomeric Compounds

NASA Astrophysics Data System (ADS)

Furmanova, Nina G.

1981-08-01

Data on the structures of potentially proto-, metallo-, and carbono-tropic compounds, obtained mainly by X-ray diffraction, are surveyed. The results of neutron and electron diffraction studies have also been partly used. It is shown that a characteristic feature of all the systems considered is the formation of hydrogen or secondary bonds ensuring the contribution of both possible tautomeric forms to the structure. Systematic consideration of the experimental data leads to the conclusion that there is a close relation between the crystal structure and the dynamic behaviour of the molecules in solution and that secondary and hydrogen bonds play a significant role in the tautomeric transition. The bibliography includes 152 references.

Diffraction leveraged modulation of X-ray pulses using MEMS-based X-ray optics

DOEpatents

Lopez, Daniel; Shenoy, Gopal; Wang, Jin; Walko, Donald A.; Jung, Il-Woong; Mukhopadhyay, Deepkishore

2016-08-09

A method and apparatus are provided for implementing Bragg-diffraction leveraged modulation of X-ray pulses using MicroElectroMechanical systems (MEMS) based diffractive optics. An oscillating crystalline MEMS device generates a controllable time-window for diffraction of the incident X-ray radiation. The Bragg-diffraction leveraged modulation of X-ray pulses includes isolating a particular pulse, spatially separating individual pulses, and spreading a single pulse from an X-ray pulse-train.

Hydrogen Atomic Positions of O-H···O Hydrogen Bonds in Solution and in the Solid State: The Synergy of Quantum Chemical Calculations with ¹H-NMR Chemical Shifts and X-ray Diffraction Methods.

PubMed

Siskos, Michael G; Choudhary, M Iqbal; Gerothanassis, Ioannis P

2017-03-07

The exact knowledge of hydrogen atomic positions of O-H···O hydrogen bonds in solution and in the solid state has been a major challenge in structural and physical organic chemistry. The objective of this review article is to summarize recent developments in the refinement of labile hydrogen positions with the use of: (i) density functional theory (DFT) calculations after a structure has been determined by X-ray from single crystals or from powders; (ii) ¹H-NMR chemical shifts as constraints in DFT calculations, and (iii) use of root-mean-square deviation between experimentally determined and DFT calculated ¹H-NMR chemical shifts considering the great sensitivity of ¹H-NMR shielding to hydrogen bonding properties.

Neutron and X-ray total scattering study of hydrogen disorder in fully hydrated hydrogrossular, Ca3Al2(O4H4)3

NASA Astrophysics Data System (ADS)

Keen, David A.; Keeble, Dean S.; Bennett, Thomas D.

2018-04-01

The structure of fully hydrated grossular, or katoite, contains an unusual arrangement of four O-H bonds within each O4 tetrahedra. Neutron and X-ray total scattering from a powdered deuterated sample have been measured to investigate the local arrangement of this O4D4 cluster. The O-D bond length determined directly from the pair distribution function is 0.954 Å, although the Rietveld-refined distance between average O and D positions was slightly smaller. Reverse Monte Carlo refinement of supercell models to the total scattering data show that other than the consequences of this correctly determined O-D bond length, there is little to suggest that the O4D4 structure is locally significantly different from that expected based on the average structure determined solely from Bragg diffraction.

Equation of state and pressure induced amorphization of beta-boron from X-ray measurements up to 100 GPa.

PubMed

Sanz, Delia Nieto; Loubeyre, Paul; Mezouar, Mohamed

2002-12-09

The equation of state of boron has been measured up to 100 GPa by single-crystal x-ray diffraction with helium as the pressure transmitting medium. Rhombohedral beta-boron is the stable structure up to 100 GPa under hydrostatic conditions. Nonhydrostatic stress stabilizes a different rhombohedral structure. At about 100 GPa a pressure-induced amorphization is observed. The amorphous phase can be quenched to ambient pressure. An explanation is proposed based on the different stability under pressure between intraicosahedra and intericosahedra bonds.

Crystal structure and X-ray photoemission spectroscopic study of A{sub 2}LaMO{sub 6} [A=Ba, Ca; M=Nb, Ta

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dutta, Alo, E-mail: alo_dutta@yahoo.com; Saha, Sujoy; Kumari, Premlata

2015-09-15

The X-ray photoemission spectroscopic (XPS) study of the double perovskite oxides A{sub 2}LaMO{sub 6} [A=Ba, Ca; M=Nb, Ta] synthesized by the solid-state reaction technique has been carried out to investigate the nature of the chemical state of the constituent ions and the bonding between them. The Rietveld refinement of the X-ray diffraction patterns suggests the monoclinic crystal structure of all the materials at room temperature. The negative and positive chemical shifts of the core level XPS spectrum of O-1s and Nb-3d{sub 3/2}/Ta-4f{sub 5/2} respectively suggest the covalent bonding between Nb/Ta cations and O ion. The change of the bonding strengthmore » between the anion and the cations from one material to another has been analyzed. The vibrational property of the materials is investigated using the room temperature Raman spectra. A large covalency of Ta-based compound than Nb compound is confirmed from the relative shifting of the Raman modes of the materials. - Graphical abstract: Crystal structure of two perovskite oxides CLN and CLT is investigated. XPS study confirms the two different co-ordination environments of Ca and covalent bonding between B-site cations and O-ion. - Highlights: • Ordered perovskite structure obtained by Rietveld refinement of XRD patterns. • Study of nature of chemical bonding by X-ray photoemission spectroscopy. • Opposite chemical shift of d-states of Nb/Ta with respect to O. • Covalent bonding between d-states of Nb/Ta and O. • Relative Raman shifts of CLN and CLT substantiate the more covalent character of Ta than Nb.« less

Cocrystals of Kemp’s triacid. Part III: Structure of hydrogen-bonded complex of Kemp’s triacid with 1,1,3,3-tetramethylguanidine studied by X-ray and FT-IR methods

NASA Astrophysics Data System (ADS)

Huczyński, Adam; Ratajczak-Sitarz, Małgorzata; Katrusiak, Andrzej; Brzezinski, Bogumil

2008-12-01

The 2:2 hydrogen-bonded complex between Kemp's triacid (KTA) and 1,1,3,3-tetramethylguanidine (TMG) has been synthesised and studied by X-ray diffraction and by FT-IR spectroscopy. Cocrystals of KTA-TMG belong to the monoclinic system and crystallize in the space group is P21 with a = 10.5017(3) Å, b = 7.9504(3) Å, c = 11.8910(4) Å, β = 104.004(4)° and Z = 2. The ring of the KTA monoanion molecule exhibits a chair conformation with all three carboxylic groups in the axial positions and all three methyl groups in the equatorial positions. In the crystal of the complex, cooperative systems involving inter- and intra-molecular hydrogen bonds are formed. In the solid state two protonated TMG molecules and two deprotonated KTA molecules form a dimer in which three-dimensional hydrogen-bonded networks are found.

Application of valence-to-core X-ray emission spectroscopy for identification and estimation of amount of carbon covalently bonded to chromium in amorphous Cr-C coatings prepared by magnetron sputtering

NASA Astrophysics Data System (ADS)

Safonov, V. A.; Habazaki, H.; Glatzel, P.; Fishgoit, L. A.; Drozhzhin, O. A.; Lafuerza, S.; Safonova, O. V.

2018-01-01

Cr-C coatings containing different amount of carbon ranging from ∼5 to 50 at.% were prepared by the direct current (DC) magnetron sputtering on a polished substrate of polycrystalline silicon. The thickness of the samples was about 400 nm. We characterized the composition and the structure of the as-received coatings and those annealed at 500 °C by X-ray diffraction (XRD), Energy dispersion X-ray spectroscopy (EDX) and valence-to-core X-ray emission spectroscopy (vtc-XES) methods As follows from XRD measurements, the samples with the carbon content above 35 at.% do not demonstrate any sign of the long-range order and annealing at 500 °C does not change their crystallinity. The vtc-XES curves of the as-prepared and annealed samples can be fitted as a superposition of corresponding spectra of chromium metal and chromium carbide (Cr3C2) phases. After the annealing, the content of carbides in the samples (and, correspondingly, the content of covalently bonded carbon) somewhat increases. This suggests that the as-received coatings contain a certain amount of carbon that is not covalently bonded to chromium (most likely, elemental carbon) and their annealing at 500 °C transforms this carbon into the additional (of the order of 2-5 at.%) amount of chromium carbide compounds. It deserves mentioning that for Cr-C coatings prepared by the electrochemical deposition from Cr(III) electrolytes containing organic compounds we have not observed changes in the vtc-X-ray emission spectra after similar annealing. This suggests that electrochemical deposition method in contrast to magnetron sputtering technique even at low temperatures favors the formation of only covalently bonded carbon.

Structural studies of crystalline forms of triamterene with carboxylic acid, GRAS and API molecules

PubMed Central

Rehman, Abida

2018-01-01

Pharmaceutical salt solvates (dimethyl sulfoxide, DMSO) of the drug triamterene with the coformers acetic, succinic, adipic, pimelic, azelaic and nicotinic acid and ibuprofen are prepared by liquid-assisted grinding and solvent-evaporative crystallization. The modified ΔpK a rule as proposed by Cruz-Cabeza [(2012 ▸). CrystEngComm, 14, 6362–6365] is in close agreement with the results of this study. All adducts were characterized by X-ray diffraction and thermal analytical techniques, including single-crystal X-ray diffraction, powder X-ray diffraction, differential scanning calorimetry and thermal gravimetric analysis. Hydrogen-bonded motifs combined to form a variety of extended tapes and sheets. Analysis of the crystal structures showed that all adducts existed as salt solvates and contained the amino­pyridinium–carboxyl­ate heterodimer, except for the solvate containing triamterene, ibuprofen and DMSO, as a result of the presence of a strong and stable hemitriamterenium duplex. A search of the Cambridge Structural Database (CSD 5.36, Version 1.18) to determine the frequency of occurrence of the putative supramolecular synthons found in this study showed good agreement with previous work. PMID:29755747

X-ray diffraction, FTIR, UV-VIS and SEM studies on chromium (III) complexes

NASA Astrophysics Data System (ADS)

Mishra, Ashutosh; Dwivedi, Jagrati; Shukla, Kritika

2015-06-01

Five Chromium (III) complexes have been prepared using Schiff base ligands which derived from benzoin and five different amino acids (H2N-R). Samples were characterized by XRD, FTIR, UV-VIS and SEM method. X-Ray diffraction pattern analyzed that all chromium (III) complexes have hexagonal structure and crystalline, in nature, using Bruker D8 Advance instrument. Using VERTAX 70, FTIR spectroscopy reveals that Samples have (C=N), (C-O), (M-N) and (M-O) bonds in the range of 4000-400cm-1. UV-VIS spectroscopy give information that samples absorb the visible light which is in the range of 380-780nm. For this, Lambda 960 spectrometer used. SEM is designed for studying of the solid objects, using JEOL JSM 5600 instrument.

Solid state characterization and crystal structure from X-ray powder diffraction of two polymorphic forms of ranitidine base.

PubMed

de Armas, Héctor Novoa; Peeters, Oswald M; Blaton, Norbert; Van Gyseghem, Elke; Martens, Johan; Van Haele, Gerrit; Van Den Mooter, Guy

2009-01-01

Ranitidine hydrochloride (RAN-HCl), a known anti-ulcer drug, is the product of reaction between HCl and ranitidine base (RAN-B). RAN-HCl has been extensively studied; however this is not the case of the RAN-B. The solid state characterization of RAN-B polymorphs has been carried out using different analytical techniques (microscopy, thermal analysis, Fourier transform infrared spectrometry in the attenuated total reflection mode, (13)C-CPMAS-NMR spectroscopy and X-ray powder diffraction). The crystal structures of RAN-B form I and form II have been determined using conventional X-ray powder diffraction in combination with simulated annealing and whole profile pattern matching, and refined using rigid-body Rietveld refinement. RAN-B form I is a monoclinic polymorph with cell parameters: a = 7.317(2), b = 9.021(2), c = 25.098(6) A, beta = 95.690(1) degrees and space group P2(1)/c. The form II is orthorhombic: a = 31.252(4), b = 13.052(2), c = 8.0892(11) A with space group Pbca. In RAN-B polymorphs, the nitro group is involved in a strong intramolecular hydrogen bond responsible for the existence of a Z configuration in the enamine portion of the molecules. A tail to tail packing motif can be denoted via intermolecular hydrogen bonds. The crystal structures of RAN-B forms are compared to those of RAN-HCl polymorphs. RAN-B polymorphs are monotropic polymorphic pairs. (c) 2008 Wiley-Liss, Inc. and the American Pharmacists Association

Synthesis, crystal structure and characterization of a new organic-inorganic hybrid material 4-(ammonium methyl) pipyridinium hexachloro stanate (II) trihydrate

NASA Astrophysics Data System (ADS)

Lassoued, Mohamed Saber; Abdelbaky, Mohammed S. M.; Lassoued, Abdelmajid; Ammar, Salah; Gadri, Abdellatif; Ben Salah, Abdelhamid; García-Granda, Santiago

2018-03-01

The present paper undertakes the study of (C6H16N2) SnCl6·3H2O which is a new hybrid compound. It was prepared and characterized by single crystal X-ray diffraction, X-ray powder, Hirshfeld surface, Spectroscopy measurement, thermal study and photoluminescence properties. The single crystal X-ray diffraction studies revealed that the compound crystallizes in monoclinic Cc space group with cell parameters a = 8.3309(9) Å, b = 22.956(2) Å, c = 9.8381(9) Å, β = 101.334(9) ° and Z = 4. The atomic arrangement shows an alternation of organic and inorganic entities. The cohesion between these entities is performed via Nsbnd H⋯Cl, Nsbnd H⋯O, Osbnd H⋯Cl and Osbnd H⋯O hydrogen bonding to form a three-dimensional network. Hirshfeld surface analysis was used to investigate intermolecular interactions, as well 2D finger plots were conducted to reveal the contribution of these interactions in the crystal structure quantitatively. The X-ray powder is in agreement with the X-ray structure. Scanning electron microscope (SEM) was carried out. Furthermore, the room temperature infrared (IR) spectrum of the title compound was recorded and analyzed on the basis of data found in the literature. Solid state 13C NMR spectrum shows four signals, confirming the solid state structure determined by X-ray diffraction. Besides, the thermal analysis studies were performed, but no phase transition was found in the temperature range between 30 and 450 °C. The optical and PL properties of the compound were investigated in the solid state at room temperature and exhibited three bands at 348 and 401 cm-1 and a strong fluorescence at 480 nm.

Environment-friendly wood fibre composite with high bonding strength and water resistance

PubMed Central

Ji, Xiaodi; Dong, Yue; Nguyen, Tat Thang; Chen, Xueqi

2018-01-01

With the growing depletion of wood-based materials and concerns over emissions of formaldehyde from traditional wood fibre composites, there is a desire for environment-friendly binders. Herein, we report a green wood fibre composite with specific bonding strength and water resistance that is superior to a commercial system by using wood fibres and chitosan-based adhesives. When the mass ratio of solid content in the adhesive and absolute dry wood fibres was 3%, the bonding strength and water resistance of the wood fibre composite reached the optimal level, which was significantly improved over that of wood fibre composites without adhesive and completely met the requirements of the Chinese national standard GB/T 11718-2009. Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) characterizations revealed that the excellent performance of the binder might partly be due to the amide linkages and hydrogen bonding between wood fibres and the chitosan-based adhesive. We believe that this strategy could open new insights into the design of environment-friendly wood fibre composites with high bonding strength and water resistance for multifunctional applications. PMID:29765653

Environment-friendly wood fibre composite with high bonding strength and water resistance

NASA Astrophysics Data System (ADS)

Ji, Xiaodi; Dong, Yue; Nguyen, Tat Thang; Chen, Xueqi; Guo, Minghui

2018-04-01

With the growing depletion of wood-based materials and concerns over emissions of formaldehyde from traditional wood fibre composites, there is a desire for environment-friendly binders. Herein, we report a green wood fibre composite with specific bonding strength and water resistance that is superior to a commercial system by using wood fibres and chitosan-based adhesives. When the mass ratio of solid content in the adhesive and absolute dry wood fibres was 3%, the bonding strength and water resistance of the wood fibre composite reached the optimal level, which was significantly improved over that of wood fibre composites without adhesive and completely met the requirements of the Chinese national standard GB/T 11718-2009. Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) characterizations revealed that the excellent performance of the binder might partly be due to the amide linkages and hydrogen bonding between wood fibres and the chitosan-based adhesive. We believe that this strategy could open new insights into the design of environment-friendly wood fibre composites with high bonding strength and water resistance for multifunctional applications.

A new silica-infiltrated Y-TZP obtained by the sol-gel method.

PubMed

Campos, T M B; Ramos, N C; Machado, J P B; Bottino, M A; Souza, R O A; Melo, R M

2016-05-01

The aim of this study was to evaluate silica infiltration into dental zirconia (VITA In-Ceram 2000 YZ, Vita Zahnfabrik) and its effects on zirconia's surface characteristics, structural homogeneity and bonding to a resin cement. Infiltration was performed by immersion of the pre-sintered zirconia specimens in silica sols for five days (ZIn). Negative (pure zirconia specimens, ZCon-) and positive controls (specimens kept in water for 5 days, ZCon+) were also performed. After sintering, the groups were evaluated by X-ray diffraction (XRD), grazing angle X-ray diffraction (DRXR), scanning electron microscopy (SEM), contact angle measurements, optical profilometry, biaxial flexural test and shear bonding test. Weibull analysis was used to determine the Weibull modulus (m) and characteristic strength (σ0) of all groups. There were no major changes in strength for the infiltrated group, and homogeneity (m) was also increased. A layer of ZrSiO4 was formed on the surface. The bond strength to resin cement was improved after zirconia infiltration, acid conditioning and the use of an MDP primer. The sol-gel method is an efficient and simple method to increase the homogeneity of zirconia. Infiltration also improved bonding to resin cement. The performance of a zirconia infiltrated by silica gel improved in at least two ways: structural homogeneity and bonding to resin cement. The infiltration is simple to perform and can be easily managed in a prosthesis laboratory. Copyright © 2016 Elsevier Ltd. All rights reserved.

Controlling superstructural ordering in the clathrate-I Ba 8 M 16 P 30 (M = Cu, Zn) through the formation of metal–metal bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dolyniuk, J.; Whitfield, P. S.; Lee, K.

2017-01-01

Order–disorder–order phase transitions in the clathrate-I Ba8Cu16P30 were induced and controlled by aliovalent substitutions of Zn into the framework. Unaltered Ba8Cu16P30 crystallizes in an ordered orthorhombic (Pbcn) clathrate-I superstructure that maintains complete segregation of metal and phosphorus atoms over 23 different crystallographic positions in the clathrate framework. The driving force for the formation of this Pbcn superstructure is the avoidance of Cu–Cu bonds. This superstructure is preserved upon aliovalent substitution of Zn for Cu in Ba8Cu16-xZnxP30 with 0 < x < 1.6 (10% Zn/Mtotal), but vanishes at greater substitution concentrations. Higher Zn concentrations (up to 35% Zn/Mtotal) resulted in themore » additional substitution of Zn for P in Ba8M16+yP30-y (M = Cu, Zn) with 0 ≤ y ≤ 1. This causes the formation of Cu–Zn bonds in the framework, leading to a collapse of the orthorhombic superstructure into the more common cubic subcell of clathrate-I (Pm[3 with combining macron]n). In the resulting cubic phases, each clathrate framework position is jointly occupied by three different elements: Cu, Zn, and P. Detailed structural characterization of the Ba–Cu–Zn–P clathrates-I via single crystal X-ray diffraction, joint synchrotron X-ray and neutron powder diffractions, pair distribution function analysis, electron diffraction and high-resolution electron microscopy, along with elemental analysis, indicates that local ordering is present in the cubic clathrate framework, suggesting the evolution of Cu–Zn bonds. For the compounds with the highest Zn content, a disorder–order transformation is detected due to the formation of another superstructure with trigonal symmetry and Cu–Zn bonds in the clathrate-I framework. It is shown that small changes in the composition, synthesis, and crystal structure have significant impacts on the structural and transport properties of Zn-substituted Ba8Cu16P30.« less

Cl⋯N weak interactions. Conformational analysis of imidazol-2-ylum heterocycles bearing N-β-chloroethyl and N-vinyl pendant groups

NASA Astrophysics Data System (ADS)

Rodríguez-López, Germán; Montes-Tolentino, Pedro; Sánchez-Ruiz, Sonia; Villaseñor-Granados, Tayde Osvaldo; Flores-Parra, Angelina

2017-11-01

Enantiomerically pure and racemic mixtures of β-chloroethylamines hydrochlorides with one and two stereogenic centres were used to synthesise 1,4-dialkyl-1,3-diimines, which in turn gave place to a series of imidazolium chlorides and tetraphenylborates bearing pendant N-β-chloroethyl substituents (sbnd CHEt-CH2Cl; sbnd CHMe-CHPhCl). Stereoselective dehydrochlorination of imidazolium compounds afforded in good yield the corresponding heterocycles bearing N-vinyl groups (-CEt=CH2; -CMe=CHPh). The volume of the N-substituents provides a steric screening of the cationic ring. The structure of the new compounds was determined by IR, mass spectra, NMR and X-ray diffraction analyses as well as DFT calculations of the optimized geometries. Uncommon stabilising intramolecular Cl⋯N weak interactions are described, together with H⋯Cl and H···π hydrogen bonds. The existence of the non-covalent weak intramolecular bonds was deduced from the X-ray diffraction analysis and confirmed by calculations of the electrostatic potential, electronic density distributions and the maps of the Laplacian functions of the electronic density.

Air and moisture stable covalently-bonded tin(ii) coordination polymers.

PubMed

de Lima, G M; Walton, R I; Clarkson, G J; Bitzer, R S; Ardisson, J D

2018-06-05

Four covalently-bonded tin(ii) coordination polymers, (1)-(4), were hydrothermally prepared in aqueous alkaline media by the reactions of SnSO4 with 1,2,4,5-benzenetetracarboxylic acid (1), 1,3,5-benzenetricarboxylic acid (2), 4-hydroxypyridine-2,6-dicarboxylic acid (3), and 1,3,5-cyclohexanetricarboxylic acid (4). All products were structurally authenticated by single-crystal X-ray diffraction, and the number of different tin centres and their oxidation states were confirmed by 119Sn Mössbauer spectroscopy. In addition, the comparison between experimental and simulated X-ray powder diffraction patterns confirmed the authenticity of the samples. Our crystallographic results for (1)-(4) show that the Sn(ii) centres are tetracoordinated and exhibit distorted disphenoidal geometries, corroborating the presence of one stereochemically active lone electron pair at each metal site. Products (1) and (2) display bi-dimensional polymeric structures, (3) exhibits a one-dimensional architecture, whereas (4) shows a remarkable three-dimensional coordination network. Hirshfeld surface and supramolecular analyses for the repeating units of (1)-(4) were also performed in order to identify structurally important non-covalent interactions.

New supramolecular cocrystal of 2-amino-5-chloropyridine with 3-methylbenzoic acids: Syntheses, structural characterization, Hirshfeld surfaces and quantum chemical investigations

NASA Astrophysics Data System (ADS)

Thanigaimani, Kaliyaperumal; Khalib, Nuridayanti Che; Temel, Ersin; Arshad, Suhana; Razak, Ibrahim Abdul

2015-11-01

2-amino-5-chloropyridine: 3-methylbenzoic acid [(2A5CP) (3MBA)] (I) cocrystal was synthesized and its single crystal was grown by slow evaporation technique. The structure of the grown crystal was elucidated by using single crystal X-ray diffraction technique. The cocrystal belongs to the monoclinic crystallographic system with space group P21/c, Z = 4, and a = 13.3155 (5) Å, b = 5.5980 (2) Å, c = 18.3787 (7) Å, β = 110.045 (2)°. The crystal structure is stabilized by Npyridine-H•••Odbnd C, Cdbnd O-H•••Npyridine and C-H⋯O type hydrogen bonding interactions. The presence of unionized -COOH functional group in the cocrystal was identified both by spectral methods and X-ray structural analysis. The experimental studies obtained by using the methods of single crystal X-ray analysis, powder X-ray diffraction (PXRD) analysis, FTIR, 1H NMR and 13C NMR spectroscopies confirmed the predicted cocrystal. The supramolecular assembly of the cocrystal was analyzed and discussed. The molecular geometry, vibrational frequencies of the compound in the ground state were calculated by using the density functional theory (DFT) method with 6-311++G (d,p) basis set and were compared with the experimental data. Additionally, HOMO-LUMO energy gap, natural bond orbital (NBO) analysis and nonlinear optical (NLO) properties of the compound were performed at B3LYP/6-311++G (d,p) level. Hirshfeld surfaces were used to confirm the existence of inter-molecular interactions in the compound.

Structural studies on choline-carboxylate bio-ionic liquids by x-ray scattering and molecular dynamics.

PubMed

Tanzi, Luana; Ramondo, Fabio; Caminiti, Ruggero; Campetella, Marco; Di Luca, Andrea; Gontrani, Lorenzo

2015-09-21

We report a X-ray diffraction and molecular dynamics study on three choline-based bio-ionic liquids, choline formate, [Ch] [For], choline propanoate, [Ch][Pro], and choline butanoate, [Ch][But]. For the first time, this class of ionic liquids has been investigated by X-ray diffraction. Experimental and theoretical structure factors have been compared for each term of the series. Local structural organization has been obtained from ab initio calculations through static models of isolated ion pairs and dynamic simulations of small portions of liquids through twelve, ten, and nine ion pairs for [Ch][For], [Ch][Pro], and [Ch][But], respectively. All the theoretical models indicate that cations and anions are connected by strong hydrogen bonding and form stable ion pairs in the liquid that are reminiscent of the static ab initio ion pairs. Different structural aspects may affect the radial distribution function, like the local structure of ion pairs and the conformation of choline. When small portions of liquids have been simulated by dynamic quantum chemical methods, some key structural features of the X-ray radial distribution function were well reproduced whereas the classical force fields here applied did not entirely reproduce all the observed structural features.

Structural studies on choline-carboxylate bio-ionic liquids by x-ray scattering and molecular dynamics

NASA Astrophysics Data System (ADS)

Tanzi, Luana; Ramondo, Fabio; Caminiti, Ruggero; Campetella, Marco; Di Luca, Andrea; Gontrani, Lorenzo

2015-09-01

We report a X-ray diffraction and molecular dynamics study on three choline-based bio-ionic liquids, choline formate, [Ch] [For], choline propanoate, [Ch][Pro], and choline butanoate, [Ch][But]. For the first time, this class of ionic liquids has been investigated by X-ray diffraction. Experimental and theoretical structure factors have been compared for each term of the series. Local structural organization has been obtained from ab initio calculations through static models of isolated ion pairs and dynamic simulations of small portions of liquids through twelve, ten, and nine ion pairs for [Ch][For], [Ch][Pro], and [Ch][But], respectively. All the theoretical models indicate that cations and anions are connected by strong hydrogen bonding and form stable ion pairs in the liquid that are reminiscent of the static ab initio ion pairs. Different structural aspects may affect the radial distribution function, like the local structure of ion pairs and the conformation of choline. When small portions of liquids have been simulated by dynamic quantum chemical methods, some key structural features of the X-ray radial distribution function were well reproduced whereas the classical force fields here applied did not entirely reproduce all the observed structural features.

Pressure-tuning of bond-directional exchange interactions and magnetic frustration in hyperhoneycomb iridate β-Li 2IrO 3

DOE PAGES

Veiga, L. S. I.; Etter, M.; Glazyrin, K.; ...

2017-10-10

Here, we explore the response of Ir 5d orbitals to pressure in β-Li 2IrO 3, a hyperhoneycomb iridate in proximity to a Kitaev quantum spin-liquid (QSL) ground state. X-ray absorption spectroscopy reveals a reconstruction of the electronic ground state below 2 GPa, the same pressure range where x-ray magnetic circular dichroism shows an apparent collapse of magnetic order. The electronic reconstruction, which manifests a reduction in the effective spin-orbit interaction in 5d orbitals, pushes β-Li 2IrO 3 further away from the pure J eff = 1/2 limit. Although lattice symmetry is preserved across the electronic transition, x-ray diffraction shows amore » highly anisotropic compression of the hyperhoneycomb lattice which affects the balance of bond-directional Ir-Ir exchange interactions driven by spin-orbit coupling at Ir sites. An enhancement of symmetric anisotropic exchange over Kitaev and Heisenberg exchange interactions seen in theoretical calculations that use precisely this anisotropic Ir-Ir bond compression provides one possible route to the realization of a QSL state in this hyperhoneycomb iridate at high pressures.« less

Pressure tuning of bond-directional exchange interactions and magnetic frustration in the hyperhoneycomb iridate β -Li2IrO3

NASA Astrophysics Data System (ADS)

Veiga, L. S. I.; Etter, M.; Glazyrin, K.; Sun, F.; Escanhoela, C. A.; Fabbris, G.; Mardegan, J. R. L.; Malavi, P. S.; Deng, Y.; Stavropoulos, P. P.; Kee, H.-Y.; Yang, W. G.; van Veenendaal, M.; Schilling, J. S.; Takayama, T.; Takagi, H.; Haskel, D.

2017-10-01

We explore the response of Ir 5 d orbitals to pressure in β -Li2IrO3 , a hyperhoneycomb iridate in proximity to a Kitaev quantum spin-liquid (QSL) ground state. X-ray absorption spectroscopy reveals a reconstruction of the electronic ground state below 2 GPa, the same pressure range where x-ray magnetic circular dichroism shows an apparent collapse of magnetic order. The electronic reconstruction, which manifests a reduction in the effective spin-orbit interaction in 5 d orbitals, pushes β -Li2IrO3 further away from the pure Jeff=1 /2 limit. Although lattice symmetry is preserved across the electronic transition, x-ray diffraction shows a highly anisotropic compression of the hyperhoneycomb lattice which affects the balance of bond-directional Ir-Ir exchange interactions driven by spin-orbit coupling at Ir sites. An enhancement of symmetric anisotropic exchange over Kitaev and Heisenberg exchange interactions seen in theoretical calculations that use precisely this anisotropic Ir-Ir bond compression provides one possible route to the realization of a QSL state in this hyperhoneycomb iridate at high pressures.

Comparison of different bonding techniques for efficient strain transfer using piezoelectric actuators

NASA Astrophysics Data System (ADS)

Ziss, Dorian; Martín-Sánchez, Javier; Lettner, Thomas; Halilovic, Alma; Trevisi, Giovanna; Trotta, Rinaldo; Rastelli, Armando; Stangl, Julian

2017-04-01

In this paper, strain transfer efficiencies from a single crystalline piezoelectric lead magnesium niobate-lead titanate substrate to a GaAs semiconductor membrane bonded on top are investigated using state-of-the-art x-ray diffraction (XRD) techniques and finite-element-method (FEM) simulations. Two different bonding techniques are studied, namely, gold-thermo-compression and polymer-based SU8 bonding. Our results show a much higher strain-transfer for the "soft" SU8 bonding in comparison to the "hard" bonding via gold-thermo-compression. A comparison between the XRD results and FEM simulations allows us to explain this unexpected result with the presence of complex interface structures between the different layers.

Comparison of different bonding techniques for efficient strain transfer using piezoelectric actuators

PubMed Central

Ziss, Dorian; Martín-Sánchez, Javier; Lettner, Thomas; Halilovic, Alma; Trevisi, Giovanna; Trotta, Rinaldo; Rastelli, Armando; Stangl, Julian

2017-01-01

In this paper, strain transfer efficiencies from a single crystalline piezoelectric lead magnesium niobate-lead titanate substrate to a GaAs semiconductor membrane bonded on top are investigated using state-of-the-art x-ray diffraction (XRD) techniques and finite-element-method (FEM) simulations. Two different bonding techniques are studied, namely, gold-thermo-compression and polymer-based SU8 bonding. Our results show a much higher strain-transfer for the “soft” SU8 bonding in comparison to the “hard” bonding via gold-thermo-compression. A comparison between the XRD results and FEM simulations allows us to explain this unexpected result with the presence of complex interface structures between the different layers. PMID:28522879

Comparison of different bonding techniques for efficient strain transfer using piezoelectric actuators.

PubMed

Ziss, Dorian; Martín-Sánchez, Javier; Lettner, Thomas; Halilovic, Alma; Trevisi, Giovanna; Trotta, Rinaldo; Rastelli, Armando; Stangl, Julian

2017-04-01

In this paper, strain transfer efficiencies from a single crystalline piezoelectric lead magnesium niobate-lead titanate substrate to a GaAs semiconductor membrane bonded on top are investigated using state-of-the-art x-ray diffraction (XRD) techniques and finite-element-method (FEM) simulations. Two different bonding techniques are studied, namely, gold-thermo-compression and polymer-based SU8 bonding. Our results show a much higher strain-transfer for the "soft" SU8 bonding in comparison to the "hard" bonding via gold-thermo-compression. A comparison between the XRD results and FEM simulations allows us to explain this unexpected result with the presence of complex interface structures between the different layers.

Acemetacin cocrystal structures by powder X-ray diffraction.

PubMed

Bolla, Geetha; Chernyshev, Vladimir; Nangia, Ashwini

2017-05-01

Cocrystals of acemetacin drug (ACM) with nicotinamide (NAM), p -aminobenzoic acid (PABA), valerolactam (VLM) and 2-pyridone (2HP) were prepared by melt crystallization and their X-ray crystal structures determined by high-resolution powder X-ray diffraction. The powerful technique of structure determination from powder data (SDPD) provided details of molecular packing and hydrogen bonding in pharmaceutical cocrystals of acemetacin. ACM-NAM occurs in anhydrate and hydrate forms, whereas the other structures crystallized in a single crystalline form. The carboxylic acid group of ACM forms theacid-amide dimer three-point synthon R 3 2 (9) R 2 2 (8) R 3 2 (9) with three different syn amides (VLM, 2HP and caprolactam). The conformations of the ACM molecule observed in the crystal structures differ mainly in the mutual orientation of chlorobenzene fragment and the neighboring methyl group, being anti (type I) or syn (type II). ACM hydrate, ACM-NAM, ACM-NAM-hydrate and the piperazine salt of ACM exhibit the type I conformation, whereas ACM polymorphs and other cocrystals adopt the ACM type II conformation. Hydrogen-bond interactions in all the crystal structures were quantified by calculating their molecular electrostatic potential (MEP) surfaces. Hirshfeld surface analysis of the cocrystal surfaces shows that about 50% of the contribution is due to a combination of strong and weak O⋯H, N⋯H, Cl⋯H and C⋯H interactions. The physicochemical properties of these cocrystals are under study.

Acemetacin cocrystal structures by powder X-ray diffraction

PubMed Central

Bolla, Geetha

2017-01-01

Cocrystals of acemetacin drug (ACM) with nicotinamide (NAM), p-aminobenzoic acid (PABA), valerolactam (VLM) and 2-pyridone (2HP) were prepared by melt crystallization and their X-ray crystal structures determined by high-resolution powder X-ray diffraction. The powerful technique of structure determination from powder data (SDPD) provided details of molecular packing and hydrogen bonding in pharmaceutical cocrystals of acemetacin. ACM–NAM occurs in anhydrate and hydrate forms, whereas the other structures crystallized in a single crystalline form. The carboxylic acid group of ACM forms theacid–amide dimer three-point synthon R 3 2(9)R 2 2(8)R 3 2(9) with three different syn amides (VLM, 2HP and caprolactam). The conformations of the ACM molecule observed in the crystal structures differ mainly in the mutual orientation of chlorobenzene fragment and the neighboring methyl group, being anti (type I) or syn (type II). ACM hydrate, ACM—NAM, ACM–NAM-hydrate and the piperazine salt of ACM exhibit the type I conformation, whereas ACM polymorphs and other cocrystals adopt the ACM type II conformation. Hydrogen-bond interactions in all the crystal structures were quantified by calculating their molecular electrostatic potential (MEP) surfaces. Hirshfeld surface analysis of the cocrystal surfaces shows that about 50% of the contribution is due to a combination of strong and weak O⋯H, N⋯H, Cl⋯H and C⋯H interactions. The physicochemical properties of these cocrystals are under study. PMID:28512568

Evaluation of the residual stresses in 95wt%Al2O3-5wt% SiC wear protection coating using X-Ray diffraction technique

NASA Astrophysics Data System (ADS)

Mahmoud, Adel K.; Hammoudi, Zaid S.; Student Samah Rasheed, M. Sc.

2018-02-01

This paper aims to measuring the residual stresses practically in wear protection coatings using the sin2ψ method according to X-ray diffraction technique. The wear protection coatings used in this study was composite coating 95wt% Al2O3-5wt% SiC, while bond coat was AlNi alloy produced by using flame spraying technique on the mild steel substrate. The diffraction angle, 2θ, is measured experimentally and then the lattice spacing is calculated from the diffraction angle, and the known X-ray wavelength using Bragg’s Law. Once the dspacing values are known, they can be plotted versus sin2ψ, (ψ is the tilt angle). In this paper, stress measurement of the samples that exhibit a linear behavior as in the case of a homogenous isotropic sample in a biaxial stress state is included. The plot of dspacing versus sin2ψ is a straight line which slope is proportional to stress. On the other hand, the second set of samples showed oscillatory dspacing versus sin2ψ behaviour. The oscillatory behaviour indicates the presence of inhomogeneous stress distribution. In this case the X-ray elastic constants must be used instead of Young’s modulus (E) and Poisson ratio (ν)values. These constants can be obtained from the literature for a given material and reflection combination. The value of the residual stresses for the present coating calculated was compressive stresses (-325.6758MPa).

1-Pentyl-3-(4-methoxy-1-naphthoyl)indole and 2-(2-methoxy-phenyl)-1-(1-pentyl-1 H-indol-3-yl)-ethanone: X-ray structures and computational studies

NASA Astrophysics Data System (ADS)

Nycz, Jacek E.; Malecki, Grzegorz; Zawiazalec, Marcin; Pazdziorek, Tadeusz; Skop, Patrycja

2010-12-01

1-Pentyl-3-(4-methoxy-1-naphthoyl)indole (shortly named JWH-081) ( 1) and 2-(2-methoxy-phenyl)-1-(1-pentyl-1 H-indol-3-yl)-ethanone (shortly named JWH-250) ( 2), are examples of cannabinoids which were characterized by FTIR, UV-Vis, multinuclear NMR spectroscopy and single crystal X-ray diffraction method. The geometries of the studied compounds were optimized in singlet states using the density functional theory (DFT) method with B3LYP functional. Electronic spectra were calculated by TDDFT method. In general, the predicted bond lengths and angles are in a good agreement with the values based on the X-ray crystal structure data.

Hirshfeld atom refinement.

PubMed

Capelli, Silvia C; Bürgi, Hans-Beat; Dittrich, Birger; Grabowsky, Simon; Jayatilaka, Dylan

2014-09-01

Hirshfeld atom refinement (HAR) is a method which determines structural parameters from single-crystal X-ray diffraction data by using an aspherical atom partitioning of tailor-made ab initio quantum mechanical molecular electron densities without any further approximation. Here the original HAR method is extended by implementing an iterative procedure of successive cycles of electron density calculations, Hirshfeld atom scattering factor calculations and structural least-squares refinements, repeated until convergence. The importance of this iterative procedure is illustrated via the example of crystalline ammonia. The new HAR method is then applied to X-ray diffraction data of the dipeptide Gly-l-Ala measured at 12, 50, 100, 150, 220 and 295 K, using Hartree-Fock and BLYP density functional theory electron densities and three different basis sets. All positions and anisotropic displacement parameters (ADPs) are freely refined without constraints or restraints - even those for hydrogen atoms. The results are systematically compared with those from neutron diffraction experiments at the temperatures 12, 50, 150 and 295 K. Although non-hydrogen-atom ADPs differ by up to three combined standard uncertainties (csu's), all other structural parameters agree within less than 2 csu's. Using our best calculations (BLYP/cc-pVTZ, recommended for organic molecules), the accuracy of determining bond lengths involving hydrogen atoms from HAR is better than 0.009 Å for temperatures of 150 K or below; for hydrogen-atom ADPs it is better than 0.006 Å(2) as judged from the mean absolute X-ray minus neutron differences. These results are among the best ever obtained. Remarkably, the precision of determining bond lengths and ADPs for the hydrogen atoms from the HAR procedure is comparable with that from the neutron measurements - an outcome which is obtained with a routinely achievable resolution of the X-ray data of 0.65 Å.

Hirshfeld atom refinement

PubMed Central

Capelli, Silvia C.; Bürgi, Hans-Beat; Dittrich, Birger; Grabowsky, Simon; Jayatilaka, Dylan

2014-01-01

Hirshfeld atom refinement (HAR) is a method which determines structural parameters from single-crystal X-ray diffraction data by using an aspherical atom partitioning of tailor-made ab initio quantum mechanical molecular electron densities without any further approximation. Here the original HAR method is extended by implementing an iterative procedure of successive cycles of electron density calculations, Hirshfeld atom scattering factor calculations and structural least-squares refinements, repeated until convergence. The importance of this iterative procedure is illustrated via the example of crystalline ammonia. The new HAR method is then applied to X-ray diffraction data of the dipeptide Gly–l-Ala measured at 12, 50, 100, 150, 220 and 295 K, using Hartree–Fock and BLYP density functional theory electron densities and three different basis sets. All positions and anisotropic displacement parameters (ADPs) are freely refined without constraints or restraints – even those for hydrogen atoms. The results are systematically compared with those from neutron diffraction experiments at the temperatures 12, 50, 150 and 295 K. Although non-hydrogen-atom ADPs differ by up to three combined standard uncertainties (csu’s), all other structural parameters agree within less than 2 csu’s. Using our best calculations (BLYP/cc-pVTZ, recommended for organic molecules), the accuracy of determining bond lengths involving hydrogen atoms from HAR is better than 0.009 Å for temperatures of 150 K or below; for hydrogen-atom ADPs it is better than 0.006 Å2 as judged from the mean absolute X-ray minus neutron differences. These results are among the best ever obtained. Remarkably, the precision of determining bond lengths and ADPs for the hydrogen atoms from the HAR procedure is comparable with that from the neutron measurements – an outcome which is obtained with a routinely achievable resolution of the X-ray data of 0.65 Å. PMID:25295177

Preparation, electronic structure, and chemical bonding of lead-free (1 - x)(K0.5Bi0.5)TiO3- xBaTiO3 solid solution

NASA Astrophysics Data System (ADS)

Sasikumar, S.; Saravanan, R.; Saravanakumar, S.; Robert, M. Charles

2018-01-01

Polycrystalline lead-free (1 - x)(K0.5Bi0.5)TiO3- xBaTiO3, ((1 - x)KBT- xBT) ( x = 0.00, 0.08, 0.12) ceramics were synthesized via solid-state reaction method. The powder X-ray diffraction (PXRD) and structural refinement results confirm that a single-phase tetragonal structure with space group P4mm. Charge density distribution inside the unit cell of (1 - x)KBT- xBT was investigated by the maximum entropy method. Charge density analysis reveals the reduction in ionic nature along K/Bi-O bond and enhancement of covalent nature along Ti-O bond with the addition of BaTiO3. The charge density distribution studies done using maximum entropy method for (1 - x)KBT- xBT have not been done so far. The surface morphology study was done using scanning electron microscopy (SEM). Energy dispersive X-rays spectra (EDS) were used to investigate the elemental compositions present in the system. The dielectric constant and loss tangent were studied as a function of frequency. The dielectric constant and loss were decreased with increase of frequency. Room temperature dielectric constant ( ɛ) and loss (tan δ) were measured for x = 0.00 about 511 and 0.51, respectively, at a frequency of 10 kHz.

Synthesis, spectral characterization and structural studies of a novel O, N, O donor semicarbazone and its binuclear copper complex with hydrogen bond stabilized lattice

NASA Astrophysics Data System (ADS)

Layana, S. R.; Saritha, S. R.; Anitha, L.; Sithambaresan, M.; Sudarsanakumar, M. R.; Suma, S.

2018-04-01

A novel O,N,O donor salicylaldehyde-N4-phenylsemicarbazone, (H2L) has been synthesized and physicochemically characterized. Detailed structural studies of H2L using single crystal X-ray diffraction technique reveals the existence of intra and inter molecular hydrogen bonding interactions, which provide extra stability to the molecule. We have successfully synthesized a binuclear copper(II) complex, [Cu2(HL)2(NO3)(H2O)2]NO3 with phenoxy bridging between the two copper centers. The complex was characterized by elemental analysis, magnetic susceptibility and conductivity measurements, FT-IR, UV-Visible, mass and EPR spectral methods. The grown crystals of the copper complex were employed for the single crystal X-ray diffraction studies. The complex possesses geometrically different metal centers, in which the ligand coordinates through ketoamide oxygen, azomethine nitrogen and deprotonated phenoxy oxygen. The extensive intermolecular hydrogen bonding interactions of the coordinated and the lattice nitrate groups interconnect the complex units to form a 2D supramolecular assembly. The ESI mass spectrum substantiates the existence of 1:1 complex. The g values obtained from the EPR spectrum in frozen DMF suggest dx2 -y2 ground state for the unpaired electron.

Synthesis and structural characterization of (C sub 5 Me sub 5 )Zr(R) sub 2 (L) sub n sup + complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crowther, D.J.; Jordan, R.F.; Baenziger, N.C.

1990-09-01

The reaction of (C{sub 5}Me{sub 5})Zr(CH{sub 3}){sub 3} with ((C{sub 5}H{sub 4}Me){sub 2}Fe)(BPh{sub 4}) in THF yields ((C{sub 5}Me{sub 5})Zr(CH{sub 3}){sub 2}(THF){sub 2})(BPh{sub 4}) (1) via oxidative cleavage of a Zr-CH{sub 3} bond. X-ray diffraction reveals that the cation of 1 adopts a square-pyramidal/four-legged piano-stool structure with cis CH{sub 3} groups. The orientations of the THF ligands and the Zr-O bond distances suggest that Zr-O {pi}-bonding is important for at least one of the THF ligands. Data for 1: a = 14.551 (2) {angstrom}, b = 15.191 (4) {angstrom}, c = 17.852 (19) {angstrom}, {beta} = 92.26 (3){degree}, V =more » 3,943 (6) {angstrom}{sup 3}, Z = 4 in space group P2{sub 1}/c. Reaction of 1 with excess dmpe in THF solution yields ((C{sub 5}Me{sub 5})Zr(CH{sub 3}){sub 2}(dmpe)(THF))(BPh{sub 4}) (2), which also has been characterized by X-ray diffraction.« less

The nature of intermediate-range order in Ge-As-S glasses : results from reverse Monte Carlo modeling.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soyer-Uzun, S.; Benmore, C. J.; Siewenie, J. E.

2010-01-01

The experimental neutron and x-ray diffraction data for stoichiometric and S-deficient Ge{sub x}As{sub x}S{sub 100-2x} glasses with x = 18.2, 25.0, and 33.3 at.% have been modeled simultaneously using the reverse Monte Carlo (RMC) technique. Nearest-neighbor coordination environments, as obtained in previous x-ray absorption spectroscopy and diffraction experiments, have been employed as short-range order constraints in these simulations. The large scale three-dimensional structural models thus obtained from RMC simulation are used to investigate the nature and compositional evolution of intermediate-range structural order in these ternary glasses. The intermediate-range structural order is controlled by (1) a corner-shared three-dimensional network of AsS{submore » 3} pyramids and GeS{sub 4} tetrahedra in the stoichiometric Ge{sub 18.2}As{sub 18.2}S{sub 63.6} glass, (2) a heterogeneous structure that consists of homopolar bonded As-rich regions coexisting with a GeS{sub 2} network in the S-deficient Ge{sub 25}As{sub 25}S{sub 50} glass, and (3) a homogeneous structure resulting from the disruption of the topological continuity of the GeS{sub 2} network and As-rich clusters regions due to the formation of Ge-As bonds in the most S-deficient Ge{sub 33.3}As{sub 33.3}S{sub 33.3} glass. This scenario of the compositional evolution of intermediate-range structural order is consistent with and provides an atomistic explanation of the corresponding evolution in the position, width and intensity of the first sharp diffraction peak and the magnitude of small angle scattering in these glasses.« less

Micro X-ray diffraction analysis of thin films using grazing-exit conditions.

PubMed

Noma, T; Iida, A

1998-05-01

An X-ray diffraction technique using a hard X-ray microbeam for thin-film analysis has been developed. To optimize the spatial resolution and the surface sensitivity, the X-ray microbeam strikes the sample surface at a large glancing angle while the diffracted X-ray signal is detected with a small (grazing) exit angle. Kirkpatrick-Baez optics developed at the Photon Factory were used, in combination with a multilayer monochromator, for focusing X-rays. The focused beam size was about 10 x 10 micro m. X-ray diffraction patterns of Pd, Pt and their layered structure were measured. Using a small exit angle, the signal-to-background ratio was improved due to a shallow escape depth. Under the grazing-exit condition, the refraction effect of diffracted X-rays was observed, indicating the possibility of surface sensitivity.

Thermal Expansion Behavior in TcO2. Toward Breaking the Tc-Tc Bond.

PubMed

Reynolds, Emily; Zhang, Zhaoming; Avdeev, Maxim; Thorogood, Gordon J; Poineau, Frederic; Czerwinski, Kenneth R; Kimpton, Justin A; Kennedy, Brendan J

2017-08-07

The structure of TcO 2 between 25 and 1000 °C has been determined in situ using X-ray powder diffraction methods and is found to remain monoclinic in space group P2 1 /c. Thermal expansion in TcO 2 is highly anisotropic, with negative thermal expansion of the b axis observed above 700 °C. This is the result of an anomalous expansion along the a axis that is a consequence of weakening of the Tc-Tc bonds.

Crystallographic perturbations to valence charge density and hydrogen-surface interactions

NASA Astrophysics Data System (ADS)

Ciston, James W.

The subject of surfaces has been the epicenter of numerous studies in recent years, particularly with respect to applications in catalysis, thin films, and self-assembly of nanostructures where the surface-to-volume ratio is large. Understanding how the atomic structure of materials differs at surfaces where the atoms are far less constrained can yield fundamental insight into these interesting nanoscale phenomena. Quantum surface crystallography takes this one step further in an attempt to experimentally measure the structure of the electrons themselves, which is of greater importance than atomic positions in determining material properties. We report a procedure for obtaining a much better initial parameterization of the charge density than what is possible from a neutral atom model. This procedure involves the parameterization of a bulk charge density model in terms of simple variables such as bond lengths, which can then be transferred to the problem of interest, for instance a surface. Parameterization is accomplished through the fitting of Density Functional Theory calculations of a variety of crystal distortions to a bond-centered pseudoatom (BCPA) model. This parameterized model can then be applied to surfaces or for other problems where an initial higher-order model is needed without the addition of any extra fitted parameters. Through the use of the BCPA model, we report a three-dimensional charge density refinement from x-ray diffraction intensities of the Si (001) 2x1H surface. By properly accounting for the covalent bonding effects in the silicon structure, we were able to stably refine the positions of hydrogen atoms at this surface in three dimensions, which had never before been accomplished for any surface. In addition, we found experimentally an increased, slightly localized bond density of approximately 0.31 electrons between each Si atom pair at the surface. Both the atomic positions and the charge density were found to be in remarkably good agreement with density functional theory (DFT) calculations. The BCPA model was also applied to an experimental refinement of the local charge density at the Si (111) 7x7 surface utilizing a combination of x-ray and high energy electron diffraction. By perturbing about the bond-centered pseudoatom model, we found experimentally that the adatoms were in an anti-bonding state with the atoms directly below. We were also able to experimentally refine a charge transfer of 0.26+/-0.04 e- from each adatom site to the underlying layers. This was the first statistically significant refinement of site-specific bonding information at any surface utilizing x-ray diffraction data. Precession electron diffraction (PED) is a technique which is gaining increasing interest due to its ease of use and reduction of the dynamical scattering problem in electron diffraction. To further investigate the usefulness of this technique, we performed a systematic study of the effect of precession angle on the mineral andalusite where the semiangle was varied from 6.5 to 32 mrad in five discrete steps. We have shown that the intensities of kinematically forbidden reflections decayed exponentially as the precession semiangle (ϕ) was increased. Additionally, we have determined that charge density effects were best observed at moderately low angles (6.5-13 mrad) even though PED patterns became more kinematical in nature as the precession angle was increased further. We have also shown that the amount of interpretable information provided by direct methods phase inversion of the diffraction data increases monotonically but non-systematically as ϕ increases. We report an experimental and theoretical analysis of the ✓3x✓3-R30° and 2x2 reconstructions on the MgO (111) surface combining transmission electron microscopy, x-ray photoelectron spectroscopy, and reasonably accurate density functional calculations using the meta-GGA functional TPSS. We have not only conclusively solved the atomic structures of these reconstructions, but have developed a kinetic model for an evolutionary pathway between structures driven entirely by exchange of water molecules between the surface and the environment that does not require the cations to move when the structure transforms. This is the first time an experimentally and theoretically supported kinetic model has described not only all of the structures in a series on a single oxide surface, but also describes why none of the structures pass through the thermodynamically most stable configuration. Lastly, we have investigated the observability of valence bonding effects in aberration-corrected high resolution electron microscopy (HREM) images along the [010] projection of the mineral Forsterite (Mg2SiO 4). Direct observability of bonding effects would be both faster and less ambiguous than the refinement of similar features against diffraction data. Through analysis of simulated high resolution electron microscopy images, we have determined that bonding effects should be observable at levels approaching 20% of the total contrast. Initial experimental results for this material system have also been presented.

A porous Cd(II) metal-organic framework with high adsorption selectivity for CO2 over CH4

NASA Astrophysics Data System (ADS)

Zhu, Chunlan

2017-05-01

Metal-organic frameworks (MOFs) have attracted a lot of attention in recent decades. We applied a semi-rigid four-carboxylic acid linker to assemble with Cd(II) ions to generate a novel microporous Cd(II) MOF material. Single crystal X-ray diffraction study reveals the different two dimension (2D) layers can be further packed together with an AB fashion by hydrogen bonds (O4sbnd H4⋯O7 = 1.863 Å) to construct a three dimension (3D) supermolecular architecture. The resulting sample can be synthesized under solvothermal reactions successfully, which exhibits high selectivity adsorption of CO2 over CH4 at room temperature. In addition, the obtained sample was characterized by thermal gravimetric analyses (TGA), Fourier-transform infrared spectra (FT-IR), elemental analysis (CHN) and powder X-ray diffraction (PXRD).

Structure and bonding in beta-HMX-characterization of a trans-annular N...N interaction.

PubMed

Zhurova, Elizabeth A; Zhurov, Vladimir V; Pinkerton, A Alan

2007-11-14

Chemical bonding in the beta-phase of the 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) crystal based on the experimental electron density obtained from X-ray diffraction data at 20 K, and solid state theoretical calculations, has been analyzed in terms of the quantum theory of atoms in molecules. Features of the intra- and intermolecular bond critical points and the oxygen atom lone-pair locations are discussed. An unusual N...N bonding interaction across the 8-membered ring has been discovered and characterized. Hydrogen bonding, O...O and O...C intermolecular interactions are reported. Atomic charges and features of the electrostatic potential are discussed.

High pressure Raman and single crystal X-ray diffraction of the alkali/calcium carbonate, shortite

NASA Astrophysics Data System (ADS)

Williams, Q. C.; Vennari, C.; O'Bannon, E. F., III

2015-12-01

Raman and synchrotron-based single crystal x-ray diffraction data have been collected on shortite (Na2Ca2(CO3)3) up to 10 GPa at 300 K. Shortite is of geological importance due to its presence in the ground-mass of kimberlites, and the alkaline-/carbon-rich character of kimberlitic eruptions. This investigation focuses on shortite's high pressure behavior and is relevant to the behavior of alkali-carbonate systems within Earth's upper mantle. X-ray data demonstrate that shortite's symmetry remains stable at high pressures—retaining orthorhombic C crystal system (Amm2) up to 10 GPa; diffraction data show a 12% volume decrease from room pressure, and a bulk modulus of 71.0(3) GPa. These also demonstrate that the c-axis is twice as compressible as the a- and b-axes. This anisotropic compression is likely due to the orientation of the relatively stiff carbonate groups, a third of which are oriented close to the plane of the a- and b-axes, c axis compression primarily involves the compaction of the 9-fold coordinate sodium and calcium polyhedral. The two distinct carbonate sites within the unit cell give rise to two Raman symmetric stretching modes of the symmetric stretch; the carbonate group stretching vibration which is close to in plane with the a- and b-axes shifts at 3.75 cm-1/GPa as opposed to the carbonate groups which is closer to in plane with the b- and c-axes which shift at 4.25 cm-1/GPa. This furthers evidence for anisotropic compression observed using x-ray diffraction--as the carbonate in plane with the a- and b-axes is compressed, the strength of oxygen bonds along the c-axis with the cations increases, thus decreasing the pressure shift of the mode. The out of plane bending vibration shifts at -0.48 cm-1/GPa, indicating an enhanced interaction of the oxygens with the cations. The multiple in plane bending modes all shift positively, as do at the low frequency lattice modes, indicating that major changes in bonding do not occur up to 10 GPa. The data collected indicates that this phase is stable at 300 K to 10 GPa. The anisotropic compaction of this alkali-rich carbonate appears to be governed by the orientation of the sodium sites, thus the behavior of alkali-rich carbonates within the kimberlitic systems is likely dependent on the bonding and local geometry of alkali cations.

Redetermination of the borax structure from laboratory X-ray data at 145 K

PubMed Central

Gainsford, Graeme J.; Kemmitt, Tim; Higham, Caleb

2008-01-01

The title compound, sodium tetraborate decahydrate (mineral name: borax), Na2[B4O5(OH)4]·8H2O, has been studied previously using X-ray [Morimoto (1956). Miner. J. 2, 1–18] and neutron [Levy & Lisensky (1978). Acta Cryst. B34, 3502–3510] diffraction data. The structure contains tetra­borate anions [B4O5(OH)4]2− with twofold rotation symmetry, which form hydrogen-bonded chains, and [Na(H2O)6] octa­hedra that form zigzag chains [Na(H2O)4/2(H2O)2/1]. The O—H bond distances obtained from the present redetermination at 145 K are shorter than those in the neutron study by an average of 0.127 (19) Å. PMID:21202161

Phase transition and intramolecular hydrogen bonding in nitro derivatives of ortho-hydroxy acetophenones

NASA Astrophysics Data System (ADS)

Filarowski, A.; Kochel, A.; Koll, A.; Bator, G.; Mukherjee, S.

2006-03-01

The crystal structures of two ortho-hydroxy aryl ketones (5-chloro-3-nitro-2-hydroxyacetophenone, 5-methyl-3-nitro-2-hydroxyacetophenone and the complex 5-chloro-3-nitro-2-hydroxyacetophenone with 2-aminobenzoic acid (anthranilic acid)) were determined by X-ray diffraction. The existence of an intramolecular hydrogen bond of enol character between the hydroxyl and acetyl groups was found by the X-ray method. The enol character was also confirmed by DFT (B3LYP/6-31+G(d,p)) calculations. A phase transition was found at 138 K in 5-chloro-3-nitro-2-hydroxyacetophenone. This phase transition was investigated by differential scanning calorimetry (DSC), dilatometry, and the dielectric method. A study of the nitro-group dynamics in the ortho-hydroxy acetophenones was carried out with DFT (B3LYP/6-31+G(d,p)) calculations.

Self-assembled Nano-layering at the Adhesive interface.

PubMed

Yoshida, Y; Yoshihara, K; Nagaoka, N; Hayakawa, S; Torii, Y; Ogawa, T; Osaka, A; Meerbeek, B Van

2012-04-01

According to the 'Adhesion-Decalcification' concept, specific functional monomers within dental adhesives can ionically interact with hydroxyapatite (HAp). Such ionic bonding has been demonstrated for 10-methacryloyloxydecyl dihydrogen phosphate (MDP) to manifest in the form of self-assembled 'nano-layering'. However, it remained to be explored if such nano-layering also occurs on tooth tissue when commercial MDP-containing adhesives (Clearfil SE Bond, Kuraray; Scotchbond Universal, 3M ESPE) were applied following common clinical application protocols. We therefore characterized adhesive-dentin interfaces chemically, using x-ray diffraction (XRD) and energy-dispersive x-ray spectroscopy (EDS), and ultrastructurally, using (scanning) transmission electron microscopy (TEM/STEM). Both adhesives revealed nano-layering at the adhesive interface, not only within the hybrid layer but also, particularly for Clearfil SE Bond (Kuraray), extending into the adhesive layer. Since such self-assembled nano-layering of two 10-MDP molecules, joined by stable MDP-Ca salt formation, must make the adhesive interface more resistant to biodegradation, it may well explain the documented favorable clinical longevity of bonds produced by 10-MDP-based adhesives.

Metal-ion interactions with carbohydrates. Crystal structure and FT-IR study of the SmCl3-ribose complex.

PubMed

Lu, Yan; Guo, Jianyu

2006-04-10

A single-crystal of SmCl3.C5H10O5.5H2O was obtained from methanol-water solution and its structure determined by X-ray. Two forms of the complex as a pair of anomers and related conformers were found in the single-crystal in a disordered state. One ligand is alpha-D-ribopyranose in the 4C1 conformation and the other one is beta-D-ribopyranose. The anomeric ratio is 1:1. Both ligands provide three hydroxyl groups in ax-eq-ax orientation for coordination. The Sm3+ ion is nine-coordinated with five Sm-O bonds from water molecules, three Sm-O bonds from hydroxyl groups of the D-ribopyranose and one Sm-Cl bond. The hydroxyl groups, water molecules and chloride ions form an extensive hydrogen-bond network. The IR spectral C-C, O-H, C-O, and C-O-H vibrations were observed to be shifted in the complex and the IR results are in accord with those of X-ray diffraction.

Iron Oxide Nanoparticles Employed as Seeds for the Induction of Microcrystalline Diamond Synthesis

PubMed Central

2008-01-01

Iron nanoparticles were employed to induce the synthesis of diamond on molybdenum, silicon, and quartz substrates. Diamond films were grown using conventional conditions for diamond synthesis by hot filament chemical vapor deposition, except that dispersed iron oxide nanoparticles replaced the seeding. X-ray diffraction, visible, and ultraviolet Raman Spectroscopy, energy-filtered transmission electron microscopy , electron energy-loss spectroscopy, and X-ray photoelectron spectroscopy (XPS) were employed to study the carbon bonding nature of the films and to analyze the carbon clustering around the seed nanoparticles leading to diamond synthesis. The results indicate that iron oxide nanoparticles lose the O atoms, becoming thus active C traps that induce the formation of a dense region of trigonally and tetrahedrally bonded carbon around them with the ensuing precipitation of diamond-type bonds that develop into microcrystalline diamond films under chemical vapor deposition conditions. This approach to diamond induction can be combined with dip pen nanolithography for the selective deposition of diamond and diamond patterning while avoiding surface damage associated to diamond-seeding methods.

X-ray diffraction from shock-loaded polycrystals.

PubMed

Swift, Damian C

2008-01-01

X-ray diffraction was demonstrated from shock-compressed polycrystalline metals on nanosecond time scales. Laser ablation was used to induce shock waves in polycrystalline foils of Be, 25-125 microm thick. A second laser pulse was used to generate a plasma x-ray source by irradiation of a Ti foil. The x-ray source was collimated to produce a beam of controllable diameter, which was directed at the Be sample. X-rays were diffracted from the sample, and detected using films and x-ray streak cameras. The diffraction angle was observed to change with shock pressure. The diffraction angles were consistent with the uniaxial (elastic) and isotropic (plastic) compressions expected for the loading conditions used. Polycrystalline diffraction will be used to measure the response of the crystal lattice to high shock pressures and through phase changes.

Three pharmaceuticals cocrystals of adefovir: Syntheses, structures and dissolution study

NASA Astrophysics Data System (ADS)

Zhang, Xiaoming; Sun, Fuxing; Zhang, Tingting; Jia, Jiangtao; Su, Hongmin; Wang, Chenhui; Zhu, Guangshan

2015-11-01

We report here three novel cocrystals, which are composed of adefovir as the API (Active Pharmaceutical Ingredient) with p-aminobenzoic acid (1, 2C8H12N5O4P·C7H6NO2·3H2O), 3,5-dihydroxybenzoic acid (2, C8H12N5O4P·C7H6O4·H2O) and 2,6-pyridinedicarboxlic acid (3, C8H12N5O4P·C7H5NO4) as CCFs (cocrystal formers) respectively by crystal engineering strategy. Their structures were characterized by single crystal X-ray diffraction, powder X-ray diffraction (PXRD) analysis, thermogravimetric analyses (TGA), elemental analysis (EA) and infrared spectral analysis (IR). The analysis of single crystal X-ray diffraction demonstrate that cocrystal 1 and 2 form a strong hydrogen-bonded assembly through the phosphoric acids of API with water in the lattice and carboxylic acids of CCF respectively. Cocrystal 3 is formed in which the phosphoric acid groups of API are also held by the carboxylic acid groups of CCF. The PXRD results indicate their high purity of as-synthesized samples. The TGA, EA, IR and dissolution study of API and the cocrystals were also measured and discussed.

Synthesis, characterization and dissolution of three pharmaceutical cocrystals based on deferiprone

NASA Astrophysics Data System (ADS)

Zhang, Xiaoming; Tian, Yuyang; Jia, Jiangtao; Zhang, Tingting; Zhu, Guangshan

2016-03-01

In this paper we present three new cocrystals based on deferiprone which is the first oral medicine as iron chelator. Solitary deferiprone possesses some known problems due to its good solubility and frequent dosing side effects. For these three novel co crystals, deferiprone is the active pharmaceutical ingredient (API), p-hydroxybenzoic acid (1, C7H9NO2·C7H6O3), 2, 5-dihydroxybenzoic acid (2, C7H9NO2·C7H6O4) and maleic acid (3, C7H9NO2·C4H4O4) are used as cocrystal formers (CCFs), respectively. Their structures were characterized by single crystal X-ray diffraction, powder X-ray diffraction (PXRD) analysis, thermogravimetric analyses (TGA), differential thermal analysis (DTA), elemental analysis (EA) and infrared spectral analysis (IR). Single crystal X-ray diffraction demonstrates that all three cocrystals (1-3) possess strong hydrogen-bondings assembled through hydroxyl of API and carboxylic acids of CCFs. The PXRD results indicate their high purity of as-synthesized samples. TGA, DTA, EA, IR and dissolution study of API and cocrystals were also measured and discussed, respectively. The results suggest that the cocrystals exhibit low dissolution rates comparing with solitary deferiprone, which is very advantageous for the oral medicine with frequent dosing side effects.

Single-pulse x-ray diffraction using polycapillary optics for in situ dynamic diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maddox, B. R., E-mail: maddox3@llnl.gov; Akin, M. C., E-mail: akin1@llnl.gov; Teruya, A.

2016-08-15

Diagnostic use of single-pulse x-ray diffraction (XRD) at pulsed power facilities can be challenging due to factors such as the high flux and brightness requirements for diffraction and the geometric constraints of experimental platforms. By necessity, the x-ray source is usually positioned very close, within a few inches of the sample. On dynamic compression platforms, this puts the x-ray source in the debris field. We coupled x-ray polycapillary optics to a single-shot needle-and-washer x-ray diode source using a laser-based alignment scheme to obtain high-quality x-ray diffraction using a single 16 ns x-ray pulse with the source >1 m from themore » sample. The system was tested on a Mo sample in reflection geometry using 17 keV x-rays from a Mo anode. We also identified an anode conditioning effect that increased the x-ray intensity by 180%. Quantitative measurements of the x-ray focal spot produced by the polycapillary yielded a total x-ray flux on the sample of 3.3 ± 0.5 × 10{sup 7} molybdenum Kα photons.« less

NMR crystallography of 2-acylamino-6-[1 H]-pyridones: Solid-state NMR, GIPAW computational, and single crystal X-ray diffraction studies

NASA Astrophysics Data System (ADS)

Ośmiałowski, Borys; Kolehmainen, Erkki; Ikonen, Satu; Ahonen, Kari; Löfman, Miika

2011-12-01

2-Acylamino-6-[1 H]-pyridones [acyl = RCO, where R = methyl ( 1), ethyl ( 2), iso-propyl ( 3), tert-butyl ( 4), and 1-adamantyl ( 5)] have been synthesized and characterized by NMR spectroscopy. From three congeners, 2, 3 and 5, also single crystal X-ray structures have been solved. For these derivatives GIPAW calculations acts as a "bridge" between solid-state NMR data and calculated chemical shifts based on X-ray determined geometry. In crystals all three compounds exist as pyridone tautomers possessing similar six-membered ring structure stabilized by intramolecular C dbnd O⋯HN hydrogen bond. Theoretical GIPAW calculated and experimental 13C and 15N CPMAS NMR shifts are in excellent agreement with each other.

Amorphous tantala and its relationship with the molten state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alderman, Oliver L.G.; Benmore, C. J.; Neuefeind, Joerg C.

The structure factors of molten Ta 2O 5 and Nb 2O 5 have been measured by high-energy x-ray and pulsed neutron diffraction. These are compared to transmission-mode x-ray diffraction through a self-supported 15-μm ion-beam sputtered amorphous tantala film. Atomistic models derived from the diffraction data by means of empirical potential structure refinement reveal that tantala and niobia liquids are very close to isomorphous, as confirmed by measurement of a molten mixture, Ta 0.8Nb 1.2O 5. Nonetheless, peak Nb-O bond lengths are about 1% shorter than those for Ta-O, at temperatures, T*=T/T melt, scaled to the melting points. Mean coordination numbersmore » are n MO≃5.6(1),n OM≃2.23(4) in the liquid state, and n TaO≃6.6(2),n OTa≃2.63(8) in the solid. The liquids are built from five- and six-fold M-O polyhedra which connect principally by corner sharing, with a minority of edge sharing; a-Ta 2O 5 on the other hand has a local structure more akin to the crystalline polymorphs, built primarily from six- and seven-fold polyhedra, with a larger degree of edge sharing. The structural differences between liquid and amorphous Ta 2O 5, coupled with observations of increasing peak bond lengths upon cooling, are consistent with the interpretation that the amorphous film reaches a supercooled liquidlike metastable equilibrium during deposition. In other words, the amorphous film shares a common progenitor state with a hypothetical glass quenched from a fragile melt. In addition, we show that recent classical interatomic potentials do not fully reproduce the diffraction data, and infer that inclusion of attractive (non-Coulombic) Ta-Ta interactions is important, particularly for obtaining the correct degree of edge sharing, coordination numbers, and densities. In conclusion, nanoscale inhomogeneity of the amorphous film is confirmed by the observation of small-angle x-ray scattering.« less

Amorphous tantala and its relationship with the molten state

NASA Astrophysics Data System (ADS)

Alderman, O. L. G.; Benmore, C. J.; Neuefeind, J.; Coillet, E.; Mermet, A.; Martinez, V.; Tamalonis, A.; Weber, R.

2018-04-01

The structure factors of molten T a2O5 and N b2O5 have been measured by high-energy x-ray and pulsed neutron diffraction. These are compared to transmission-mode x-ray diffraction through a self-supported 15-μm ion-beam sputtered amorphous tantala film. Atomistic models derived from the diffraction data by means of empirical potential structure refinement reveal that tantala and niobia liquids are very close to isomorphous, as confirmed by measurement of a molten mixture, T a0.8N b1.2O5 . Nonetheless, peak Nb-O bond lengths are about 1 % shorter than those for Ta-O, at temperatures, T*=T /Tmelt , scaled to the melting points. Mean coordination numbers are nM O≃5.6 (1 ) ,nO M≃2.23 (4 ) in the liquid state, and nTaO≃6.6 (2 ) ,nOTa≃2.63 (8 ) in the solid. The liquids are built from five- and six-fold M -O polyhedra which connect principally by corner sharing, with a minority of edge sharing; a-T a2O5 on the other hand has a local structure more akin to the crystalline polymorphs, built primarily from six- and seven-fold polyhedra, with a larger degree of edge sharing. The structural differences between liquid and amorphous T a2O5 , coupled with observations of increasing peak bond lengths upon cooling, are consistent with the interpretation that the amorphous film reaches a supercooled liquidlike metastable equilibrium during deposition. In other words, the amorphous film shares a common progenitor state with a hypothetical glass quenched from a fragile melt. In addition, we show that recent classical interatomic potentials do not fully reproduce the diffraction data, and infer that inclusion of attractive (non-Coulombic) Ta-Ta interactions is important, particularly for obtaining the correct degree of edge sharing, coordination numbers, and densities. Nanoscale inhomogeneity of the amorphous film is confirmed by the observation of small-angle x-ray scattering.

Amorphous tantala and its relationship with the molten state

DOE PAGES

Alderman, Oliver L.G.; Benmore, C. J.; Neuefeind, Joerg C.; ...

2018-04-01

The structure factors of molten Ta 2O 5 and Nb 2O 5 have been measured by high-energy x-ray and pulsed neutron diffraction. These are compared to transmission-mode x-ray diffraction through a self-supported 15-μm ion-beam sputtered amorphous tantala film. Atomistic models derived from the diffraction data by means of empirical potential structure refinement reveal that tantala and niobia liquids are very close to isomorphous, as confirmed by measurement of a molten mixture, Ta 0.8Nb 1.2O 5. Nonetheless, peak Nb-O bond lengths are about 1% shorter than those for Ta-O, at temperatures, T*=T/T melt, scaled to the melting points. Mean coordination numbersmore » are n MO≃5.6(1),n OM≃2.23(4) in the liquid state, and n TaO≃6.6(2),n OTa≃2.63(8) in the solid. The liquids are built from five- and six-fold M-O polyhedra which connect principally by corner sharing, with a minority of edge sharing; a-Ta 2O 5 on the other hand has a local structure more akin to the crystalline polymorphs, built primarily from six- and seven-fold polyhedra, with a larger degree of edge sharing. The structural differences between liquid and amorphous Ta 2O 5, coupled with observations of increasing peak bond lengths upon cooling, are consistent with the interpretation that the amorphous film reaches a supercooled liquidlike metastable equilibrium during deposition. In other words, the amorphous film shares a common progenitor state with a hypothetical glass quenched from a fragile melt. In addition, we show that recent classical interatomic potentials do not fully reproduce the diffraction data, and infer that inclusion of attractive (non-Coulombic) Ta-Ta interactions is important, particularly for obtaining the correct degree of edge sharing, coordination numbers, and densities. In conclusion, nanoscale inhomogeneity of the amorphous film is confirmed by the observation of small-angle x-ray scattering.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Veiga, L. S. I.; Etter, M.; Glazyrin, K.

Here, we explore the response of Ir 5d orbitals to pressure in β-Li 2IrO 3, a hyperhoneycomb iridate in proximity to a Kitaev quantum spin-liquid (QSL) ground state. X-ray absorption spectroscopy reveals a reconstruction of the electronic ground state below 2 GPa, the same pressure range where x-ray magnetic circular dichroism shows an apparent collapse of magnetic order. The electronic reconstruction, which manifests a reduction in the effective spin-orbit interaction in 5d orbitals, pushes β-Li 2IrO 3 further away from the pure J eff = 1/2 limit. Although lattice symmetry is preserved across the electronic transition, x-ray diffraction shows amore » highly anisotropic compression of the hyperhoneycomb lattice which affects the balance of bond-directional Ir-Ir exchange interactions driven by spin-orbit coupling at Ir sites. An enhancement of symmetric anisotropic exchange over Kitaev and Heisenberg exchange interactions seen in theoretical calculations that use precisely this anisotropic Ir-Ir bond compression provides one possible route to the realization of a QSL state in this hyperhoneycomb iridate at high pressures.« less

Synthesis of Fluorinated Graphene/CoAl-Layered Double Hydroxide Composites as Electrode Materials for Supercapacitors.

PubMed

Peng, Weijun; Li, Hongqiang; Song, Shaoxian

2017-02-15

CoAl-layered double hydroxide/fluorinated graphene (CoAl-LDH/FGN) composites were fabricated via a two-step hydrothermal method. The synthesized CoAl-LDH/FGN composites have been characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), and electrochemical measurements. The results indicated that the fluorinated carbon with various configuration forms were grafted onto the framework of graphene, and the C-F bond configuration and fluorine content could be tuned by the fluorination time. Most of semi-ionic C-F bonds were formed at an appropriate fluorination time and, then, converted into fluorine rich surface groups (such as CF 2 , CF 3 , etc.) which were electrochemically inactive as the fluorination time prolonged. Moreover, the CoAl-LDH/FGN composites prepared at the optimal fluorination time exhibited the highest specific capacitance (1222 F/g at 1 A/g), the best rate capability, and the most stable capacitance retention, which offered great promise as electrode materials for supercapacitors.

Crystal Structure of 17α-Dihydroequilin, C18H22O2, from Synchrotron Powder Diffraction Data and Density Functional Theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaduk, James; Gindhart, Amy; Blanton, Thomas

The crystal structure of 17α-dihydroequilin has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. 17α-dihydroequilin crystallizes in space group P212121 (#19) with a = 6.76849(1) Å, b = 8.96849(1) Å, c = 23.39031(5) Å, V = 1419.915(3) Å3, and Z = 4. Both hydroxyl groups form hydrogen bonds to each other, resulting in zig-zag chains along the b-axis. The powder diffraction pattern has been submitted to ICDD for inclusion in the Powder Diffraction File™ as the entry 00-066-1608.

Crystal structure of choline fenofibrate (Trilipix®), (C5H14NO) (C17H14ClO4)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaduk, James A.; Zhong, Kai; Gindhart, Amy M.

2016-04-04

The crystal structure of choline fenofibrate has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Choline fenofibrate crystallizes in space groupPbca(#61) witha= 12.341 03(2),b= 28.568 70(6),c= 12.025 62(2) Å,V= 4239.84(1) Å 3, andZ= 8. The hydroxyl group of the choline anion makes a strong hydrogen bond to the ionized carboxylate group of the fenofibrate anion. Together with C–H···O hydrogen bonds, these link the cations and anions into layers parallel to theac-plane. The powder pattern has been submitted to ICDD for inclusion in the Powder Diffraction File™.

Chemical Ni-C Bonding in Ni-Carbon Nanotube Composite by a Microwave Welding Method and Its Induced High-Frequency Radar Frequency Electromagnetic Wave Absorption.

PubMed

Sha, Linna; Gao, Peng; Wu, Tingting; Chen, Yujin

2017-11-22

In this work, a microwave welding method has been used for the construction of chemical Ni-C bonding at the interface between carbon nanotubes (CNTs) and metal Ni to provide a different surface electron distribution, which determined the electromagnetic (EM) wave absorption properties based on a surface plasmon resonance mechanism. Through a serial of detailed examinations, such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, and Raman spectrum, the as-expected chemical Ni-C bonding between CNTs and metal Ni has been confirmed. And the Brunauer-Emmett-Teller and surface zeta potential measurements uncovered the great evolution of structure and electronic density compared with CNTs, metal Ni, and Ni-CNT composite without Ni-C bonding. Correspondingly, except the EM absorption due to CNTs and metal Ni in the composite, another wide and strong EM absorption band ranging from 10 to 18 GHz was found, which was induced by the Ni-C bonded interface. With a thinner thickness and more exposed Ni-C interfaces, the Ni-CNT composite displayed less reflection loss.

Structure of dimethylphenyl betaine hydrochloride studied by X-ray diffraction, DFT calculation, NMR and FTIR spectra

NASA Astrophysics Data System (ADS)

Szafran, M.; Katrusiak, A.; Dega-Szafran, Z.; Kowalczyk, I.

2013-01-01

The structure of dimethylphenyl betaine hydrochloride (1) has been studied by X-ray diffraction, DFT calculations, NMR and FTIR spectra. The crystals are monoclinic, space group P21/c. In the crystal, the Cl- anion is connected with protonated betaine through the O-H⋯Cl- hydrogen bond of 2.943(2) Å. The structures in the gas phase (2) and water solution (3) have been optimized by the B3LYP/6-311++G(d,p) approach and the geometrical results have been compared with the X-ray data of 1. The FTIR spectrum of the solid compound is consistent with the X-ray results. The probable assignments of the anharmonic experimental vibrational frequencies of the investigated chloride (1) based on the calculated harmonic frequencies in water solution (3) are proposed. The correlations between the experimental 1H and 13C NMR chemical shifts (δexp) of 1 in D2O and the magnetic isotropic shielding constants (σcalc) calculated by the GIAO/B3LYP/6-311G++(d,p) approach, using the screening solvation model (COSMO), δexp = a + b σcalc, for optimized molecule 3 in water solution are linear and correctly reproduce the experimental chemical shifts.

Plutonium-uranium mixed oxide characterization by coupling micro-X-ray diffraction and absorption investigations

NASA Astrophysics Data System (ADS)

Degueldre, C.; Martin, M.; Kuri, G.; Grolimund, D.; Borca, C.

2011-09-01

Plutonium-uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The potential differences of metal redox state and microstructural developments of the matrix before and after irradiation are commonly analysed by electron probe microanalysis. In this work the structure and next-neighbor atomic environments of Pu and U oxide features within unirradiated homogeneous MOX and irradiated (60 MW d kg -1) MOX samples was analysed by micro-X-ray fluorescence (μ-XRF), micro-X-ray diffraction (μ-XRD) and micro-X-ray absorption fine structure (μ-XAFS) spectroscopy. The grain properties, chemical bonding, valences and stoichiometry of Pu and U are determined from the experimental data gained for the unirradiated as well as for irradiated fuel material examined in the center of the fuel as well as in its peripheral zone (rim). The formation of sub-grains is observed as well as their development from the center to the rim (polygonization). In the irradiated sample Pu remains tetravalent (>95%) and no (<5%) Pu(V) or Pu(VI) can be detected while the fuel could undergo slight oxidation in the rim zone. Any slight potential plutonium oxidation is buffered by the uranium dioxide matrix while locally fuel cladding interaction could also affect the redox of the fuel.

Structural studies on choline-carboxylate bio-ionic liquids by x-ray scattering and molecular dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tanzi, Luana; Ramondo, Fabio, E-mail: fabio.ramondo@univaq.it; Caminiti, Ruggero

2015-09-21

We report a X-ray diffraction and molecular dynamics study on three choline-based bio-ionic liquids, choline formate, [Ch] [For], choline propanoate, [Ch][Pro], and choline butanoate, [Ch][But]. For the first time, this class of ionic liquids has been investigated by X-ray diffraction. Experimental and theoretical structure factors have been compared for each term of the series. Local structural organization has been obtained from ab initio calculations through static models of isolated ion pairs and dynamic simulations of small portions of liquids through twelve, ten, and nine ion pairs for [Ch][For], [Ch][Pro], and [Ch][But], respectively. All the theoretical models indicate that cations andmore » anions are connected by strong hydrogen bonding and form stable ion pairs in the liquid that are reminiscent of the static ab initio ion pairs. Different structural aspects may affect the radial distribution function, like the local structure of ion pairs and the conformation of choline. When small portions of liquids have been simulated by dynamic quantum chemical methods, some key structural features of the X-ray radial distribution function were well reproduced whereas the classical force fields here applied did not entirely reproduce all the observed structural features.« less

X-Ray Diffraction Apparatus

NASA Technical Reports Server (NTRS)

Blake, David F. (Inventor); Bryson, Charles (Inventor); Freund, Friedmann (Inventor)

1996-01-01

An x-ray diffraction apparatus for use in analyzing the x-ray diffraction pattern of a sample is introduced. The apparatus includes a beam source for generating a collimated x-ray beam having one or more discrete x-ray energies, a holder for holding the sample to be analyzed in the path of the beam, and a charge-coupled device having an array of pixels for detecting, in one or more selected photon energy ranges, x-ray diffraction photons produced by irradiating such a sample with said beam. The CCD is coupled to an output unit which receives input information relating to the energies of photons striking each pixel in the CCD, and constructs the diffraction pattern of photons within a selected energy range striking the CCD.

An amyloid-forming peptide from the yeast prion Sup35 reveals a dehydrated β-sheet structure for amyloid

PubMed Central

Balbirnie, Melinda; Grothe, Robert; Eisenberg, David S.

2001-01-01

X-ray diffraction and other biophysical tools reveal features of the atomic structure of an amyloid-like crystal. Sup35, a prion-like protein in yeast, forms fibrillar amyloid assemblies intrinsic to its prion function. We have identified a polar peptide from the N-terminal prion-determining domain of Sup35 that exhibits the amyloid properties of full-length Sup35, including cooperative kinetics of aggregation, fibril formation, binding of the dye Congo red, and the characteristic cross-β x-ray diffraction pattern. Microcrystals of this peptide also share the principal properties of the fibrillar amyloid, including a highly stable, β-sheet-rich structure and the binding of Congo red. The x-ray powder pattern of the microcrystals, extending to 0.9-Å resolution, yields the unit cell dimensions of the well-ordered structure. These dimensions restrict possible atomic models of this amyloid-like structure and demonstrate that it forms packed, parallel-stranded β-sheets. The unusually high density of the crystals shows that the packed β-sheets are dehydrated, despite the polar character of the side chains. These results suggest that amyloid is a highly intermolecularly bonded, dehydrated array of densely packed β-sheets. This dry β-sheet could form as Sup35 partially unfolds to expose the peptide, permitting it to hydrogen-bond to the same peptide of other Sup35 molecules. The implication is that amyloid-forming units may be short segments of proteins, exposed for interactions by partial unfolding. PMID:11226247

Real-time X-ray Diffraction: Applications to Materials Characterization

NASA Technical Reports Server (NTRS)

Rosemeier, R. G.

1984-01-01

With the high speed growth of materials it becomes necessary to develop measuring systems which also have the capabilities of characterizing these materials at high speeds. One of the conventional techniques of characterizing materials was X-ray diffraction. Film, which is the oldest method of recording the X-ray diffraction phenomenon, is not quite adequate in most circumstances to record fast changing events. Even though conventional proportional counters and scintillation counters can provide the speed necessary to record these changing events, they lack the ability to provide image information which may be important in some types of experiment or production arrangements. A selected number of novel applications of using X-ray diffraction to characterize materials in real-time are discussed. Also, device characteristics of some X-ray intensifiers useful in instantaneous X-ray diffraction applications briefly presented. Real-time X-ray diffraction experiments with the incorporation of image X-ray intensification add a new dimension in the characterization of materials. The uses of real-time image intensification in laboratory and production arrangements are quite unlimited and their application depends more upon the ingenuity of the scientist or engineer.

Synthesis and characterization of 3-acetoxy-2-methyl-N-(phenyl)benzamide and 3-acetoxy-2-methyl-N-(4- methylphenyl)benzamide

NASA Astrophysics Data System (ADS)

Kırca, Başak Koşar; Çakmak, Şükriye; Kütük, Halil; Odabaşoğlu, Mustafa; Büyükgüngör, Orhan

2018-01-01

This study treats about two successfully synthesized secondary amide compounds 3-Acetoxy-2-methyl-N-(phenyl)benzamide, I and 3-Acetoxy-2-methyl-N-(4-methylphenyl)benzamide, II. Compounds were characterized by FTIR, 1H NMR, 13C NMR and X-ray single crystal diffraction analysis techniques. Single crystal X-ray diffraction analyses show that while I crystallized in the orthorhombic system with space group Pbca, II crystallized in the triclinic system with space group P-1 and the asymmetric unit of II consists of two crystallographically independent molecules. Lattice constants are a = 7.9713 (3) Å, b = 9.5059 (3) Å, c = 37.1762 (2) Å, Z = 8 for I and a = 7.5579 (8) Å, b = 8.8601 (8) Å, c = 23.363 (3) Å, α = 97.011 (9) °, β = 96.932 (9)°, γ = 90.051 (8)°, Z = 4 for II. Crystallographic studies also show that the supramolecular structures were stabilized by intramolecular, intermolecular hydrogen bonds and Csbnd H … π interactions for both compounds. Characteristic amide bonds were observed in IR and NMR spectra.

Pressure-induced structural transformations of the Zintl phase sodium silicide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cabrera, Raul Quesada; Salamat, Ashkan; Barkalov, Oleg I.

The high-pressure behaviour of NaSi has been studied using Raman spectroscopy and angle-dispersive synchrotron X-ray diffraction to observe the onset of structural phase transformations and potential oligomerisation into anionic Si nanoclusters with extended dimensionality. Our studies reveal a first structural transformation occurring at 8-10 GPa, followed by irreversible amorphisation above 15 GPa, suggesting the formation of Si-Si bonds with oxidation of the Si{sup -} species and reduction of Na{sup +} to metallic sodium. We have combined our experimental studies with DFT calculations to assist in the analysis of the structural behaviour of NaSi at high pressure. - Abstract: The high-pressuremore » behaviour of NaSi has been studied using Raman spectroscopy and angle-dispersive synchrotron X-ray diffraction. Our studies reveal a first structural transformation occurring at 8-10 GPa, followed by irreversible amorphisation, suggesting the formation of Si-Si bonds with oxidation of the Si{sup -} species and reduction of Na{sup +} to metallic sodium. We have combined our experimental studies with DFT calculations to assist in the analysis of the structural behaviour of NaSi at high pressure. Display Omitted« less

Single-crystal X-ray diffraction study of Fe 2SiO 4 fayalite up to 31 GPa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jin S.; Hu, Yi; Shelton, Hannah

2016-10-03

Olivine is widely believed to be the most abundant mineral in the Earth’s upper mantle. Here, we report structural refinement results for the Fe-end-member olivine, Fe 2SiO 4 fayalite, up to 31 GPa in diamond-anvil cell, using single-crystal synchrotron X-ray diffraction. Unit-cell parameters a, b, c and V, average Si–O Fe–O bond lengths, as well as Si–O Fe–O polyhedral volumes continuously decrease with increasing pressure. The pressure derivative of isothermal bulk modulus K' T0 is determined to be 4.0 (2) using third-order Birch–Murnaghan equation of state with ambient isothermal bulk modulus fixed to 135 GPa on the basis of previousmore » Brillouin measurements. The Si–O tetrahedron is stiffer than the Fe–O octahedra, and the compression mechanism is dominated by Fe–O bond and Fe–O octahedral compression. Densities of olivine along 1600 and 900 K adiabats are calculated based on this study. The existence of metastable olivine inside the cold subduction slab could cause large positive buoyancy force against subduction, slow down the subduction and possibly affect the slab geometry.« less

One-pot synthesis, quantum chemical calculations and X-ray diffraction studies of thiazolyl-coumarin hybrid compounds

NASA Astrophysics Data System (ADS)

Saeed, Aamer; Arif, Mubeen; Erben, Mauricio F.; Flörke, Ulrich; Simpson, Jim

2018-06-01

Two closely related hybrid species containing both, thiazolyl and coumarin groups, were synthesized by using two different one-pot procedures from a common precursor. The reaction of α-bromoacetylcoumarin with thioacetamide in methanol furnished 3‑(2‑methylthiazol‑4‑yl)‑2H‑chromen‑2‑one (2), whereas refluxing α‑bromoacetylcoumarin with potassium thiocyanate in ethanol afforded 3‑(2‑ethoxythiazol‑4‑yl)‑2H‑chromen‑2‑one (3). Both derivatives were fully characterized by spectroscopic methods, elemental analysis and X-ray diffraction studies. Intramolecular C4sbnd H⋯N and C5‧sbnd H⋯Odbnd C hydrogen bonds between the heterocycles determine the conformational behavior. The co-planarity of the coumarin and thiazolyl rings favors the occurrence of two remote orbital interactions involving the oxygen and nitrogen lone pairs and the corresponding σ*Csbnd H electron acceptor, as demonstrated by Natural Bond Orbital population analysis. The 2-substitution of the thiazol‑4‑yl group has little effect on the molecular structures but causes significant differences in the crystal packing of the two compounds.

Structural, spectroscopic and theoretical studies on 3,4,7,8-tetramethyl-1,10-phenantroline complex with picric acid

NASA Astrophysics Data System (ADS)

Bator, G.; Sobczyk, L.; Sawka-Dobrowolska, W.; Wuttke, J.; Pawlukojć, A.; Grech, E.; Nowicka-Scheibe, J.

2013-01-01

The almost planar molecular complex, formed by 3,4,7,8-tetramethyl-phenantroline (Me4phen) and picric acid (2,4,6-trinitrophenol, PA), has been investigated by using X-ray diffraction, vibrational spectroscopy, tunnel splitting and theoretical analysis. In the crystal of Me4phen·PA two short bifurcated hydrogen bonds N+-H···O- [2.6238(14) Å] and N+-H···N [2.6898(15) Å] are created. Infra-red spectra show the hydrogen bonds are short. The neutron backscattering spectrum of Me4phenṡPA at 3 K shows two tunneling peaks at ca. 1 and 3 μeV. The number of the peaks is consistent with X-ray diffraction studies, which disclosed the inequivalence of methyl groups in the crystal structure. The comparison of the tunnel splitting for neat Me4phen and for its complex with picric acid indicates that in the latter case the methyl groups are more strongly engaged in the intermolecular interactions, particularly with nitro group oxygen atoms of picric acid, leading to an increase of the CH3 rotational barrier height.

Structural and microstructural description of the glacial state in triphenyl phosphite from powder synchrotron X-ray diffraction data and Raman scattering investigations

NASA Astrophysics Data System (ADS)

Derollez, P.; Hernandez, O.; Hédoux, A.; Guinet, Y.; Masson, O.; Lefebvre, J.; Descamps, M.

2004-06-01

The structure and microstructure (refinement of the isotropic size and microstrain parameters) of the glacial state in triphenyl phosphite (TPP, P(OC 6H 5) 3) transformed at 222K have been determined from powder synchrotron X-ray diffraction data through a Rietveld and a Le Bail refinement, respectively. It is shown that the glacial state is composed of crystallites of the stable crystal phase coexisting with non-transformed supercooled liquid, the apparent size of the crystallites—depending on the aging temperature at which the glacial state is isothermally formed, [Phys. Rev. B 60 (1999) 9390]—being equal to 329.2(2) Å at 222K. The molecular conformation is slightly less mirror-symmetric than the one in the crystal state, and correlatively only one of the two unusual weak intermolecular C-H⋯O hydrogen bonds already observed in the latter state is encountered in the glacial one. Additional Raman scattering investigations confirm the previous result and reveal in addition that no hydrogen bonding interaction is observed neither in the glass nor in the liquid states.

Radiation damage free ghost diffraction with atomic resolution

DOE PAGES

Li, Zheng; Medvedev, Nikita; Chapman, Henry N.; ...

2017-12-21

The x-ray free electron lasers can enable diffractive structural determination of protein nanocrystals and single molecules that are too small and radiation-sensitive for conventional x-ray diffraction. However the electronic form factor may be modified during the ultrashort x-ray pulse due to photoionization and electron cascade caused by the intense x-ray pulse. For general x-ray imaging techniques, the minimization of the effects of radiation damage is of major concern to ensure reliable reconstruction of molecular structure. Here in this paper, we show that radiation damage free diffraction can be achieved with atomic spatial resolution by using x-ray parametric down-conversion and ghostmore » diffraction with entangled photons of x-ray and optical frequencies. We show that the formation of the diffraction patterns satisfies a condition analogous to the Bragg equation, with a resolution that can be as fine as the crystal lattice length scale of several Ångstrom. Since the samples are illuminated by low energy optical photons, they can be free of radiation damage.« less

Radiation damage free ghost diffraction with atomic resolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zheng; Medvedev, Nikita; Chapman, Henry N.

The x-ray free electron lasers can enable diffractive structural determination of protein nanocrystals and single molecules that are too small and radiation-sensitive for conventional x-ray diffraction. However the electronic form factor may be modified during the ultrashort x-ray pulse due to photoionization and electron cascade caused by the intense x-ray pulse. For general x-ray imaging techniques, the minimization of the effects of radiation damage is of major concern to ensure reliable reconstruction of molecular structure. Here in this paper, we show that radiation damage free diffraction can be achieved with atomic spatial resolution by using x-ray parametric down-conversion and ghostmore » diffraction with entangled photons of x-ray and optical frequencies. We show that the formation of the diffraction patterns satisfies a condition analogous to the Bragg equation, with a resolution that can be as fine as the crystal lattice length scale of several Ångstrom. Since the samples are illuminated by low energy optical photons, they can be free of radiation damage.« less

Synchrotron Radiation X-ray Diffraction Techniques Applied to Insect Flight Muscle.

PubMed

Iwamoto, Hiroyuki

2018-06-13

X-ray fiber diffraction is a powerful tool used for investigating the molecular structure of muscle and its dynamics during contraction. This technique has been successfully applied not only to skeletal and cardiac muscles of vertebrates but also to insect flight muscle. Generally, insect flight muscle has a highly ordered structure and is often capable of high-frequency oscillations. The X-ray diffraction studies on muscle have been accelerated by the advent of 3rd-generation synchrotron radiation facilities, which can generate brilliant and highly oriented X-ray beams. This review focuses on some of the novel experiments done on insect flight muscle by using synchrotron radiation X-rays. These include diffraction recordings from single myofibrils within a flight muscle fiber by using X-ray microbeams and high-speed diffraction recordings from the flight muscle during the wing-beat of live insects. These experiments have provided information about the molecular structure and dynamic function of flight muscle in unprecedented detail. Future directions of X-ray diffraction studies on muscle are also discussed.

Nontypical iodine–halogen bonds in the crystal structure of (3 E )-8-chloro-3-iodomethylidene-2,3-dihydro-1,4-oxazino[2,3,4- ij ]quinolin-4-ium triiodide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bartashevich, E. V.; Batalov, V. I.; Yushina, I. D.

2016-03-23

Two kinds of iodine–iodine halogen bonds are the focus of our attention in the crystal structure of the title salt, C 12H 8ClINO +·I 3 -, described by X-ray diffraction. The first kind is a halogen bond, reinforced by charges, between the I atom of the heterocyclic cation and the triiodide anion. The second kind is the rare case of a halogen bond between the terminal atoms of neighbouring triiodide anions. The influence of relatively weakly bound iodine inside an asymmetric triiodide anion on the thermal and Raman spectroscopic properties has been demonstrated.

Quinoline derivative containing monomeric and polymeric metal carboxylates: Synthesis, crystal structure and gas adsorption study over a 2D layered framework

NASA Astrophysics Data System (ADS)

Gayen, Saikat; Saha, Debraj; Koner, Subratanath

2018-06-01

A new supramolecular metal-carboxylate framework [Co(mqc)2]n (1), and another monomeric compound [Zn (mqc)2(H2O)] (2) (mqcH = 4-methoxy 2-quinolinecarboxylic acid) have been synthesized solvothermally and characterized by single crystal X-ray diffraction, elemental analysis, IR spectra, UV-vis spectra, powdered X-ray diffraction (PXRD) and thermogravimetric analysis. Compound 1 is a 2D coordination polymer, extended to a 3D porous supramolecular network having void space in between 2D layers. Compound 1 exhibits gas uptake capacity of N2, H2, CO2 and CH4 like small gas molecules in which moderately high uptake of H2 and CO2 takes place among the 2D MOFs. While the Zn variety, compound 2 features a one-dimensional chain like structure through strong intermolecular hydrogen-bonding.

Crystal structure, spectrum character and explosive property of a new cocrystal CL-20/DNT

NASA Astrophysics Data System (ADS)

Liu, Ke; Zhang, Gao; Luan, Jieyu; Chen, Zhiqun; Su, Pengfei; Shu, Yuanjie

2016-04-01

A new cocrystal explosive of 2,4,6,8,10,12-hexanitrohexaazaiso-wurtzitane(CL-20) and 2,5-dinitrotoluene(DNT) in a molar ratio of 1:2 has been prepared by slow solvent evaporation method. Crystal structure of the cocrystal characterized by single crystal X-ray diffraction (SXRD) reveals that the cocrystal is formed by intermolecular hydrogen bond interactions and belongs to the triclinic system with P-1 group. Moreover, the obivious differences of powder X-ray diffraction (PXRD) patterns, infrared spectroscopy and Raman spectroscopy confirm that the intermolecular interactions have great influence for the crystal structure and formation of cocrystal. The cocrystal exhibits a lower impact height of 44 cm, suggesting a substantial reduction of sensitivity in comparison with CL-20. And thermal test results showed cocrystal obtains a lower melting point than DNT, which means huge advantages in blasting engineering.

Definitive Mineralogical Analysis of Mars Analog Rocks Using the CheMin XRD/XRF Instrument

NASA Technical Reports Server (NTRS)

Blake, D. F.; Sarrazin, P.; Bish, D. L.; Feldman, S.; Chipera, S. J.; Vaniman, D. T.; Collins, S.

2004-01-01

Mineral identification is a critical component of Mars Astrobiological missions. Chemical or elemental data alone are not definitive because a single elemental or chemical composition or even a single bonding type can represent a range of substances or mineral assemblages. Minerals are defined as unique structural and compositional phases that occur naturally. There are about 15,000 minerals that have been described on Earth, all uniquely identifiable via diffraction methods. There are likely many minerals yet undiscovered on Earth, and likewise on Mars. If an unknown phase is identified on Mars, it can be fully characterized by structural (X-ray Diffraction, XRD) and elemental analysis (X-ray Fluorescence, XRF) without recourse to other data because XRD relies on the principles of atomic arrangement for its determinations. XRD is the principal means of identification and characterization of minerals on Earth.

Influence of BN fiber coatings on the interfacial structure of sapphire fiber reinforced NiAl composites

NASA Astrophysics Data System (ADS)

Reichert, K.; Wen, K.; Cremer, R.; Hu, W.; Neuschütz, D.; Gottstein, G.

2001-07-01

A new concept for a tailored fiber-matrix interface for sapphire fiber reinforced NiAl matrix composites is proposed, consisting of an initial hexagonal boron nitride (hBN) fiber coating. For this, single crystal Al 2O 3 fibers were coated with hBN by chemical vapor deposition (CVD). Following a comprehensive characterization of the CVD coating as to composition and structure by means of X-ray photoelectron spectroscopy (XPS) and grazing incidence X-ray diffraction (GIXRD), the fiber reinforced NiAl matrix composites were fabricated by diffusion bonding at 1400°C. The interfaces NiAl/BN and BN/Al 2O 3 were analyzed by scanning electron microscopy (SEM), analytical transmission electron microscopy (TEM), and selected area diffraction (SAD). An interfacial reaction between NiAl and hBN to form AlN was revealed using these analytical techniques.

X-Ray diffraction, spectroscopy and thermochemical characterization of the pharmaceutical paroxetine nitrate salt

NASA Astrophysics Data System (ADS)

Carvalho, Paulo S.; de Melo, Cristiane C.; Ayala, Alejandro P.; Ellena, Javier

2016-08-01

A comprehensive solid state study of Paroxetine nitrate hydrate, (PRX+·NO3-)H2O, is reported. This salt was characterized by a combination of methods, including Single crystal X-ray diffraction, Thermal analysis, Fourier transform infrared spectroscopy (FTIR) and Solubility measurements. (PRX+·NO3-)H2O crystallizes in the monoclinic C2 space group (Z‧ = 1) and its packing was analyzed in details, showing that the main supramolecular motif consists in a C22(4) chain formed by charge-assisted N+-H⋯O- hydrogen bonds. The salt formation and conformation features were also accuracy established via FTIR spectra. In comparison with the pharmaceutical approved (PRX+ṡCl-)ṡ0.5H2O, (PRX+ṡNO3-)ṡH2O showed a decrease of 24 °C in the drug melting peak and a slight reduction in its water solubility value.

Symmetry and charge order in Fe2OBO3 studied through polarized resonant x-ray diffraction

NASA Astrophysics Data System (ADS)

Bland, S. R.; Angst, M.; Adiga, S.; Scagnoli, V.; Johnson, R. D.; Herrero-Martín, J.; Hatton, P. D.

2010-09-01

Bond valence sum calculations have previously suggested that iron oxyborate exhibits charge order of the Fe ions with integer 2+/3+ valence states. Meanwhile transition metal oxides typically show much smaller, fractional charge disproportionations. Using resonant x-ray diffraction at the iron K edge, we find resonant features which are much larger than those ordinarily observed in charge ordered oxides. Simulations were subsequently performed using a cluster-based, monoelectronic code. The nanoscale domain structure prevents precise fitting; nevertheless the simulations confirm the diagonal charge order symmetry, as well as the unusually large charge disproportionation. We have demonstrated the conversion of linearly to nonlinearly polarized light and vice versa through full polarization analysis. Simulations show that this effect principally results from interference between the isotropic and anisotropic scattering terms. This mechanism is likely to account for similar observations in alternative systems.

Arsenolite: a quasi-hydrostatic solid pressure-transmitting medium.

PubMed

Sans, J A; Manjón, F J; Popescu, C; Muñoz, A; Rodríguez-Hernández, P; Jordá, J L; Rey, F

2016-11-30

This study reports the experimental characterization of the hydrostatic properties of arsenolite (As4O6), a molecular solid which is one of the softest minerals in the absence of hydrogen bonding. The high compressibility of arsenolite and its stability up to 15 GPa have been proved by x-ray diffraction measurements, and the progressive loss of hydrostaticity with increasing pressure up to 20 GPa has been monitored by ruby photoluminescence. Arsenolite has been found to exhibit hydrostatic behavior up to 2.5 GPa and a quasi-hydrostatic behavior up to 10 GPa at room temperature. This result opens the way to explore other molecular solids as possible quasi-hydrostatic pressure-transmitting media. The validity of arsenolite as an insulating, stable, non-penetrating and quasi-hydrostatic medium is explored by the study of the x-ray diffraction of zeolite ITQ-29 at high pressure.

Spiral chain structure of high pressure selenium-II{sup '} and sulfur-II from powder x-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujihisa, Hiroshi; Yamawaki, Hiroshi; Sakashita, Mami

2004-10-01

The structure of high pressure phases, selenium-II{sup '} (Se-II{sup '}) and sulfur-II (S-II), for {alpha}-Se{sub 8} (monoclinic Se-I) and {alpha}-S{sub 8} (orthorhombic S-I) was studied by powder x-ray diffraction experiments. Se-II{sup '} and S-II were found to be isostructural and to belong to the tetragonal space group I4{sub 1}/acd, which is made up of 16 atoms in the unit cell. The structure consisted of unique spiral chains with both 4{sub 1} and 4{sub 3} screws. The results confirmed that the structure sequence of the pressure-induced phase transitions for the group VIb elements depended on the initial molecular form. The chemicalmore » bonds of the phases are also discussed from the interatomic distances that were obtained.« less

X-ray diffraction investigations of structural modifications in In-doped tin pyrophosphates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Botez, Cristian E.; Martinez, Heber; Morris, Joshua L.

2017-08-01

Laboratory and synchrotron x-ray powder diffraction were used to investigate the structural modifications that occur upon indium doping of tin pyrophosphate. The data collected under air, vacuum, and inert gas sample environments at temperatures (T) from 50 °C to 300 °C show that regardless of the In-doping level (0 ≤ x ≤ 0.18) all InxSn1-xP2O7 samples are isomorphic (have the same P a -3 cubic crystal structure) at all temperatures and under all the conditions investigated. The cubic lattice parameter (a) increases linearly with T at all doping levels, but the “a vs. x|T“ isotherms exhibit a robust peak atmore » x = 0.1 when data are collected on samples measured in air. On the other hand, Rietveld refinements against data collected on InxSn1-xP2O7 samples yield values of OO bond lengths and POP bond angles that show no major changes at x = 0.1 at any temperature. This is significant, as the Sn0.9In0.1P2O7 (x = 0.1) compound is known to exhibit the highest proton conductivity within the series, but the microscopic details responsible for the increased proton conductivity are not understood. Finally, the peak observed in the “a vs. x|T“ curves vanishes if the measurements are taken on samples kept either under vacuum or in an inert gas environment. This is a remarkable behavior as it lends further support to our hypothesis that a key microscopic feature responsible for the large proton conductivity of the Sn0.9In0.1P2O7 compound is the enlargement of the lattice constant at x = 0.1.« less

Quantum model of catalysis based on a mobile proton revealed by subatomic x-ray and neutron diffraction studies of h-aldose reductase

PubMed Central

Blakeley, Matthew P.; Ruiz, Federico; Cachau, Raul; Hazemann, Isabelle; Meilleur, Flora; Mitschler, Andre; Ginell, Stephan; Afonine, Pavel; Ventura, Oscar N.; Cousido-Siah, Alexandra; Haertlein, Michael; Joachimiak, Andrzej; Myles, Dean; Podjarny, Alberto

2008-01-01

We present results of combined studies of the enzyme human aldose reductase (h-AR, 36 kDa) using single-crystal x-ray data (0.66 Å, 100K; 0.80 Å, 15K; 1.75 Å, 293K), neutron Laue data (2.2 Å, 293K), and quantum mechanical modeling. These complementary techniques unveil the internal organization and mobility of the hydrogen bond network that defines the properties of the catalytic engine, explaining how this promiscuous enzyme overcomes the simultaneous requirements of efficiency and promiscuity offering a general mechanistic view for this class of enzymes. PMID:18250329

Quantum model of catalysis based on a mobile proton revealed by subatomic x-ray and neutron diffraction studies of h-aldose reductase.

PubMed

Blakeley, Matthew P; Ruiz, Federico; Cachau, Raul; Hazemann, Isabelle; Meilleur, Flora; Mitschler, Andre; Ginell, Stephan; Afonine, Pavel; Ventura, Oscar N; Cousido-Siah, Alexandra; Haertlein, Michael; Joachimiak, Andrzej; Myles, Dean; Podjarny, Alberto

2008-02-12

We present results of combined studies of the enzyme human aldose reductase (h-AR, 36 kDa) using single-crystal x-ray data (0.66 A, 100K; 0.80 A, 15K; 1.75 A, 293K), neutron Laue data (2.2 A, 293K), and quantum mechanical modeling. These complementary techniques unveil the internal organization and mobility of the hydrogen bond network that defines the properties of the catalytic engine, explaining how this promiscuous enzyme overcomes the simultaneous requirements of efficiency and promiscuity offering a general mechanistic view for this class of enzymes.

Quantum Model of Catalysis Based on a Mobile Proton Revealed by Subatomic X-ray and Neutron Diffraction Studies of h-aldose Reductase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blakeley, M. P.; Ruiz, Fredrico; Cachau, Raul

2008-01-01

We present results of combined studies of the enzyme human aldose reductase (h-AR, 36 kDa) using single-crystal x-ray data (0.66 Angstroms, 100K; 0.80 Angstroms, 15K; 1.75 Angstroms, 293K), neutron Laue data (2.2 Angstroms, 293K), and quantum mechanical modeling. These complementary techniques unveil the internal organization and mobility of the hydrogen bond network that defines the properties of the catalytic engine, explaining how this promiscuous enzyme overcomes the simultaneous requirements of efficiency and promiscuity offering a general mechanistic view for this class of enzymes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chuang, Yu-Chun; Sheu, Chou-Fu; Lee, Gene-Hsiang

High-resolution X-ray diffraction experiments and atom-specific X-ray absorption experiments are applied to investigate a series of square planar complexes with the non-innocent ligand of maleonitriledithiolate (mnt), [S 2C 2(CN) 2] z-, containingM—S bonds. Four complexes of (PyH) z[M(mnt) 2] z-, whereM= Ni or Cu,z= 2 or 1 and PyH += C 5NH 6 +, were studied in order to clarify whether such one-electron oxidation–reduction, [M(mnt) 2] 2-/[M(mnt) 2] 1-, is taking place at the metal or the ligand site. Combining the techniques of metalK-,L-edge and SK-edge X-ray absorption spectroscopy with high-resolution X-ray charge density studies, it is unambiguously demonstrated thatmore » the electron redox reaction is ligand based and metal based for Ni and Cu pairs, respectively. The bonding characters in terms of topological properties associated with the bond critical points are compared between the oxidized form [ML] -and the reduced form [ML] 2-. In the case of Ni complexes, the formal oxidation state of Ni remains as Ni 2+and each mnt ligand carries a 2- charge in [Ni(mnt) 2] 2-, but only one of the ligands is formally oxidized in [Ni(mnt) 2] 1-. In contrast, in the case of Cu complexes, the mnt remains as 2- in both complexes, but the formal oxidation states of the metal are Cu 2+and Cu 3+. Bond characterizations andd-orbital populations will be presented. The complementary results of XAS, XRD and DFT calculations will be discussed. The conclusion on the redox reactions in these complexes can be firmly established.« less

"Newton's cradle" proton relay with amide-imidic acid tautomerization in inverting cellulase visualized by neutron crystallography.

PubMed

Nakamura, Akihiko; Ishida, Takuya; Kusaka, Katsuhiro; Yamada, Taro; Fushinobu, Shinya; Tanaka, Ichiro; Kaneko, Satoshi; Ohta, Kazunori; Tanaka, Hiroaki; Inaka, Koji; Higuchi, Yoshiki; Niimura, Nobuo; Samejima, Masahiro; Igarashi, Kiyohiko

2015-08-01

Hydrolysis of carbohydrates is a major bioreaction in nature, catalyzed by glycoside hydrolases (GHs). We used neutron diffraction and high-resolution x-ray diffraction analyses to investigate the hydrogen bond network in inverting cellulase PcCel45A, which is an endoglucanase belonging to subfamily C of GH family 45, isolated from the basidiomycete Phanerochaete chrysosporium. Examination of the enzyme and enzyme-ligand structures indicates a key role of multiple tautomerizations of asparagine residues and peptide bonds, which are finally connected to the other catalytic residue via typical side-chain hydrogen bonds, in forming the "Newton's cradle"-like proton relay pathway of the catalytic cycle. Amide-imidic acid tautomerization of asparagine has not been taken into account in recent molecular dynamics simulations of not only cellulases but also general enzyme catalysis, and it may be necessary to reconsider our interpretation of many enzymatic reactions.

Combining experiment and optical simulation in coherent X-ray nanobeam characterization of Si/SiGe semiconductor heterostructures

DOE PAGES

Tilka, J. A.; Park, J.; Ahn, Y.; ...

2016-07-06

Here, the highly coherent and tightly focused x-ray beams produced by hard x-ray light sources enable the nanoscale characterization of the structure of electronic materials but are accompanied by significant challenges in the interpretation of diffraction and scattering patterns. X-ray nanobeams exhibit optical coherence combined with a large angular divergence introduced by the x-ray focusing optics. The scattering of nanofocused x-ray beams from intricate semiconductor heterostructures produces a complex distribution of scattered intensity. We report here an extension of coherent xray optical simulations of convergent x-ray beam diffraction patterns to arbitrary x-ray incident angles to allow the nanobeam diffraction patternsmore » of complex heterostructures to be simulated faithfully. These methods are used to extract the misorientation of lattice planes and the strain of individual layers from synchrotron x-ray nanobeam diffraction patterns of Si/SiGe heterostructures relevant to applications in quantum electronic devices. The systematic interpretation of nanobeam diffraction patterns from semiconductor heterostructures presents a new opportunity in characterizing and ultimately designing electronic materials.« less

New Polymorph Form of Dexamethasone Acetate.

PubMed

Silva, Ronaldo Pedro da; Ambrósio, Mateus Felipe Schuchter; Piovesan, Luciana Almeida; Freitas, Maria Clara Ramalho; Aguiar, Daniel Lima Marques de; Horta, Bruno Araújo Cautiero; Epprecht, Eugenio Kahn; San Gil, Rosane Aguiar da Silva; Visentin, Lorenzo do Canto

2018-02-01

A new monohydrated polymorph of dexamethasone acetate was crystallized and its crystal structure characterized. The different analytical techniques used for describing its structural and vibrational properties were: single crystal and polycrystal X-ray diffraction, solid state nuclear magnetic resonance, infrared spectroscopy. A Hirshfeld surface analysis was carried out through self-arrangement cemented by H-bonds observed in this new polymorph. This new polymorph form appeared because of self-arrangement via classical hydrogen bonds around the water molecule. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Study of chloride ion transport of composite by using cement and starch as a binder

DOE Office of Scientific and Technical Information (OSTI.GOV)

Armynah, Bidayatul; Halide, Halmar; Zahrawani,

This study presents the chemical bonding and the structural properties of composites from accelerator chloride test migration (ACTM). The volume fractions between binder (cement and starch) and charcoal in composites are 20:80 and 60:40. The effect of the binder to the chemical composition, chemical bonding, and structural properties before and after chloride ion passing through the composites was determined by X-ray fluorescence (XRF), by Fourier transform infra-red (FTIR), and x-ray diffraction (XRD), respectively. From the XRD data, XRF data, and the FTIR data shows the amount of chemical composition, the type of binding, and the structure of composites are dependingmore » on the type of binder. The amount of chloride migration using starch as binder is higher than that of cement as a binder due to the density effects.« less

Chemical lift-off and direct wafer bonding of GaN/InGaN P-I-N structures grown on ZnO

NASA Astrophysics Data System (ADS)

Pantzas, K.; Rogers, D. J.; Bove, P.; Sandana, V. E.; Teherani, F. H.; El Gmili, Y.; Molinari, M.; Patriarche, G.; Largeau, L.; Mauguin, O.; Suresh, S.; Voss, P. L.; Razeghi, M.; Ougazzaden, A.

2016-02-01

p-GaN/i-InGaN/n-GaN (PIN) structures were grown epitaxially on ZnO-buffered c-sapphire substrates by metal organic vapor phase epitaxy using the industry standard ammonia precursor for nitrogen. Scanning electron microscopy revealed continuous layers with a smooth interface between GaN and ZnO and no evidence of ZnO back-etching. Energy Dispersive X-ray Spectroscopy revealed a peak indium content of just under 5 at% in the active layers. The PIN structure was lifted off the sapphire by selectively etching away the ZnO buffer in an acid and then direct bonded onto a glass substrate. Detailed high resolution transmission electron microscoy and grazing incidence X-ray diffraction studies revealed that the structural quality of the PIN structures was preserved during the transfer process.

Neutron diffraction reveals hydrogen bonds critical for cGMP-selective activation: Insights for cGMP-dependent protein kinase agonist design

DOE PAGES

Huang, Gilbert Y.; Gerlits, Oksana O.; Blakeley, Matthew P.; ...

2014-10-01

High selectivity of cyclic-nucleotide binding (CNB) domains for cAMP and cGMP are required for segregating signaling pathways; however, the mechanism of selectivity remains unclear. To investigate the mechanism of high selectivity in cGMP-dependent protein kinase (PKG), we determined a room-temperature joint X-ray/neutron (XN) structure of PKG Iβ CNB-B, a domain 200-fold selective for cGMP over cAMP, bound to cGMP (2.2 Å), and a low-temperature X-ray structure of CNB-B with cAMP (1.3 Å). Finally, the XN structure directly describes the hydrogen bonding interactions that modulate high selectivity for cGMP, while the structure with cAMP reveals that all these contacts are disrupted,more » explaining its low affinity for cAMP.« less

Fabrication and testing of a newly designed slit system for depth-resolved X-ray diffraction measurements

DOE PAGES

Sinsheimer, John; Bouet, Nathalie; Ghose, Sanjit; ...

2016-10-06

A new system of slits called `spiderweb slits' have been developed for depth-resolved powder or polycrystalline X-ray diffraction measurements. The slits act on diffracted X-rays to select a particular gauge volume of sample, while absorbing diffracted X-rays from outside of this volume. Although the slit geometry is to some extent similar to that of previously developed conical slits or spiral slits, this new design has advantages over the previous ones in use for complex heterogeneous materials and in situ and operando diffraction measurements. For example, the slits can measure a majority of any diffraction cone for any polycrystalline material, overmore » a continuous range of diffraction angles, and work for X-ray energies of tens to hundreds of kiloelectronvolts. In addition, the design is generated and optimized using ray-tracing simulations, and fabricated through laser micromachining. The first prototype was successfully tested at the X17A beamline at the National Synchrotron Light Source, and shows similar performance to simulations, demonstrating gauge volume selection for standard powders, for all diffraction peaks over angles of 2–10°. A similar, but improved, design will be implemented at the X-ray Powder Diffraction beamline at the National Synchrotron Light Source II.« less

Hard alpha-keratin degradation inside a tissue under high flux X-ray synchrotron micro-beam: a multi-scale time-resolved study.

PubMed

Leccia, Emilie; Gourrier, Aurélien; Doucet, Jean; Briki, Fatma

2010-04-01

X-rays interact strongly with biological organisms. Synchrotron radiation sources deliver very intense X-ray photon fluxes within micro- or submicro cross-section beams, resulting in doses larger than the MGy. The relevance of synchrotron radiation analyses of biological materials is therefore questionable since such doses, million times higher than the ones used in radiotherapy, can cause huge damages in tissues, with regard to not only DNA, but also proteic and lipid organizations. Very few data concerning the effect of very high X-ray doses in tissues are available in the literature. We present here an analysis of the structural phenomena which occur when the model tissue of human hair is irradiated by a synchrotron X-ray micro-beam. The choice of hair is supported by its hierarchical and partially ordered keratin structure which can be analysed inside the tissue by X-ray diffraction. To assess the damages caused by hard X-ray micro-beams (1 microm(2) cross-section), short exposure time scattering SAXS/WAXS patterns have been recorded at beamline ID13 (ESRF) after various irradiation times. Various modifications of the scattering patterns are observed, they provide fine insight of the radiation damages at various hierarchical levels and also unexpectedly provide information about the stability of the various hierarchical structural levels. It appears that the molecular level, i.e. the alpha helices which are stabilized by hydrogen bonds and the alpha-helical coiled coils which are stabilized by hydrophobic interactions, is more sensitive to radiation than the supramolecular architecture of the keratin filament and the filament packing within the keratin associated proteins matrix, which is stabilized by disulphide bonds. (c) 2009 Elsevier Inc. All rights reserved.

Effect of in-situ bonding system and surface modification of montmorillonite on the properties of butyl rubber/MMT composites

NASA Astrophysics Data System (ADS)

Halim, S. F.; Lawandy, S. N.; Nour, M. A.

2012-07-01

Isobutylene-isoprene rubber (IIR)/nanoclay composites were prepared by solution intercalation method. Cloisite Na+ nanoclays and organo-modified montmorillonite (OMT) Cloisite 10 A,.15 A and 20 A were used in this study. The effect of In-situ bonding system HRH (hexametylene tetramine: resorcinol: hydrated silica) on the dispersion of used nanoclays in the rubber matrix were examined by X-ray diffraction and atomic force microscopy (AFM). Characterization of the prepared composites was performed by studying the rheometeric and mechanical properties. The burning out behavior of the nanocomposites with and without the bonding system was also measured.

Dynamical scattering in coherent hard x-ray nanobeam Bragg diffraction

NASA Astrophysics Data System (ADS)

Pateras, A.; Park, J.; Ahn, Y.; Tilka, J. A.; Holt, M. V.; Kim, H.; Mawst, L. J.; Evans, P. G.

2018-06-01

Unique intensity features arising from dynamical diffraction arise in coherent x-ray nanobeam diffraction patterns of crystals having thicknesses larger than the x-ray extinction depth or exhibiting combinations of nanoscale and mesoscale features. We demonstrate that dynamical scattering effects can be accurately predicted using an optical model combined with the Darwin theory of dynamical x-ray diffraction. The model includes the highly divergent coherent x-ray nanobeams produced by Fresnel zone plate focusing optics and accounts for primary extinction, multiple scattering, and absorption. The simulation accurately reproduces the dynamical scattering features of experimental diffraction patterns acquired from a GaAs/AlGaAs epitaxial heterostructure on a GaAs (001) substrate.

Coherent x-ray diffraction imaging with nanofocused illumination.

PubMed

Schroer, C G; Boye, P; Feldkamp, J M; Patommel, J; Schropp, A; Schwab, A; Stephan, S; Burghammer, M; Schöder, S; Riekel, C

2008-08-29

Coherent x-ray diffraction imaging is an x-ray microscopy technique with the potential of reaching spatial resolutions well beyond the diffraction limits of x-ray microscopes based on optics. However, the available coherent dose at modern x-ray sources is limited, setting practical bounds on the spatial resolution of the technique. By focusing the available coherent flux onto the sample, the spatial resolution can be improved for radiation-hard specimens. A small gold particle (size <100 nm) was illuminated with a hard x-ray nanobeam (E=15.25 keV, beam dimensions approximately 100 x 100 nm2) and is reconstructed from its coherent diffraction pattern. A resolution of about 5 nm is achieved in 600 s exposure time.

Enhanced UVB emission and analysis of chemical states of Ca5(PO4)3OH:Gd3+,Pr3+ phosphor prepared by co-precipitation

NASA Astrophysics Data System (ADS)

Mokoena, P. P.; Nagpure, I. M.; Kumar, Vinay; Kroon, R. E.; Olivier, E. J.; Neethling, J. H.; Swart, H. C.; Ntwaeaborwa, O. M.

2014-08-01

Hydroxyapatite (Ca5(PO4)3OH) is a well-known bioceramic material used in medical applications because of its ability to form direct chemical bonds with living tissues. This mineral is currently used as a host for rare-earth ions (e.g. Gd3+, Pr3+, Tb3+, etc.) to prepare phosphors that can be used in light emitting devices of different types. In this study Ca5(PO4)3OH:Gd3+,Pr3+ phosphors were prepared by the co-precipitation method and were characterised by x-ray diffraction, x-ray photoelectron spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy, energy dispersive x-ray spectroscopy and photoluminescence spectroscopy. The x-ray diffraction pattern was consistent with the hexagonal phase of Ca5(PO4)3OH referenced in JCPDS card number 73-0293. The x-ray photoelectron spectroscopy data indicated that Ca2+ occupied two different lattice sites, referred to as Ca1 and Ca2. The photoluminescence data exhibited a narrowband emission located at 313 nm, which is associated with the 6P7/2→8S7/2 transition of the Gd3+ ion. This emission is classified as ultraviolet B and it is suitable for use in phototherapy lamps to treat various skin diseases. The photoluminescence intensity of the 313 nm emission was enhanced considerably by Pr3+ co-doping.

DynAMITe: a prototype large area CMOS APS for breast cancer diagnosis using x-ray diffraction measurements

NASA Astrophysics Data System (ADS)

Konstantinidis, A.; Anaxagoras, T.; Esposito, M.; Allinson, N.; Speller, R.

2012-03-01

X-ray diffraction studies are used to identify specific materials. Several laboratory-based x-ray diffraction studies were made for breast cancer diagnosis. Ideally a large area, low noise, linear and wide dynamic range digital x-ray detector is required to perform x-ray diffraction measurements. Recently, digital detectors based on Complementary Metal-Oxide- Semiconductor (CMOS) Active Pixel Sensor (APS) technology have been used in x-ray diffraction studies. Two APS detectors, namely Vanilla and Large Area Sensor (LAS), were developed by the Multidimensional Integrated Intelligent Imaging (MI-3) consortium to cover a range of scientific applications including x-ray diffraction. The MI-3 Plus consortium developed a novel large area APS, named as Dynamically Adjustable Medical Imaging Technology (DynAMITe), to combine the key characteristics of Vanilla and LAS with a number of extra features. The active area (12.8 × 13.1 cm2) of DynaMITe offers the ability of angle dispersive x-ray diffraction (ADXRD). The current study demonstrates the feasibility of using DynaMITe for breast cancer diagnosis by identifying six breast-equivalent plastics. Further work will be done to optimize the system in order to perform ADXRD for identification of suspicious areas of breast tissue following a conventional mammogram taken with the same sensor.

Resolution enhancement in coherent x-ray diffraction imaging by overcoming instrumental noise.

PubMed

Kim, Chan; Kim, Yoonhee; Song, Changyong; Kim, Sang Soo; Kim, Sunam; Kang, Hyon Chol; Hwu, Yeukuang; Tsuei, Ku-Ding; Liang, Keng San; Noh, Do Young

2014-11-17

We report that reference objects, strong scatterers neighboring weak phase objects, enhance the phase retrieval and spatial resolution in coherent x-ray diffraction imaging (CDI). A CDI experiment with Au nano-particles exhibited that the reference objects amplified the signal-to-noise ratio in the diffraction intensity at large diffraction angles, which significantly enhanced the image resolution. The interference between the diffracted x-ray from reference objects and a specimen also improved the retrieval of the phase of the diffraction signal. The enhancement was applied to image NiO nano-particles and a mitochondrion and confirmed in a simulation with a bacteria phantom. We expect that the proposed method will be of great help in imaging weakly scattering soft matters using coherent x-ray sources including x-ray free electron lasers.

High resolution crystal structure of the methylcobalamin analogues ethylcobalamin and butylcobalamin by X-ray synchrotron diffraction.

PubMed

Hannibal, Luciana; Smith, Clyde A; Smith, Jessica A; Axhemi, Armend; Miller, Abby; Wang, Sihe; Brasch, Nicola E; Jacobsen, Donald W

2009-07-20

The X-ray crystal structures of the methylcobalamin (MeCbl) analogues ethylcobalamin (EtCbl) and butylcobalamin (BuCbl) are reported. The X-ray crystal structures of EtCbl and BuCbl were obtained with some of the lowest crystallographic residuals ever achieved for cobalamins (R = 0.0468 and 0.0438, respectively). The Co-C bond distances for EtCbl and BuCbl are 2.023(2) and 2.028(4) A, whereas the Co-alpha-5,6-dimethylbenzimidazole (Co-N3B) bond distances were 2.232(1) and 2.244(1) A, respectively. Although EtCbl and BuCbl displayed a longer Co-N3B bond than that observed in the naturally occurring methylcobalamin, the orientation of the alpha-5,6-dimethylbenzimidazole moiety with respect to the corrin ring did not vary substantially among the structures. The lengthening of both Co-C and Co-N3B bonds in EtCbl and BuCbl can be attributed to the "inverse" trans influence exerted by the sigma-donating alkyl groups, typically observed in alkylcobalamins. Analysis of the molecular surface maps showed that the alkyl ligands in EtCbl and BuCbl are directed toward the hydrophobic side of the corrin ring. The corrin fold angles in EtCbl and BuCbl were determined to be 14.7 degrees and 13.1 degrees, respectively. A rough correlation exists between the corrin fold angle and the length of the Co-N3B bond, and both alkylcobalamins follow the same trend.

High Resolution Crystal Structure of the Methylcobalamin Analogs Ethylcobalamin and Butylcobalamin by X-ray Synchrotron Diffraction

PubMed Central

Hannibal, Luciana; Smith, Clyde A; Smith, Jessica A.; Axhemi, Armend; Miller, Abby; Wang, Sihe; Brasch, Nicola E.; Jacobsen, Donald W.

2009-01-01

The X-ray crystal structures of the methylcobalamin (MeCbl) analogs ethylcobalamin (EtCbl) and butylcobalamin (BuCbl) are reported. The X-ray crystal structures of EtCbl and BuCbl were obtained with some of the lowest crystallographic residuals ever achieved for cobalamins (R = 0.0468 and 0.0438, respectively). The Co-C bond distances for EtCbl and BuCbl are 2.023(2) and 2.028(4) Å, whereas the Co-α-5,6-dimethylbenzimidazole (Co-N3B) bond distances were 2.232(1) and 2.244(1) Å, respectively. Although EtCbl and BuCbl displayed a longer Co-N3B bond than that observed in the naturally occurring methylcobalamin, the orientation of the α-5,6-dimethylbenzimidazole moiety with respect to the corrin ring did not vary substantially amongst the structures. The lengthening of both Co-C and Co-N3B bonds in EtCbl and BuCbl can be attributed to the “inverse” trans influence exerted by the σ-donating alkyl groups, typically observed in alkylcobalamins. Analysis of the molecular surface maps showed that the alkyl ligands in EtCbl and BuCbl are directed towards the hydrophobic side of the corrin ring. The corrin fold angles in EtCbl and BuCbl were determined to be 14.7° and 13.1°, respectively. A rough correlation exists between the corrin fold angle and the length of the Co-N3B bond, and both alkylcobalamins follow the same trend. PMID:19545130

Pt and Ru X-ray absorption spectroscopy of PtRu anode catalysts in operating direct methanol fuel cells.

PubMed

Stoupin, Stanislav; Chung, Eun-Hyuk; Chattopadhyay, Soma; Segre, Carlo U; Smotkin, Eugene S

2006-05-25

In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides.

Synthesis, structural, conformational and pharmacological study of some amides derived from 3 -methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-amine

NASA Astrophysics Data System (ADS)

Iriepa, I.; Bellanato, J.; Gálvez, E.; Gil-Alberdi, B.

2010-07-01

Some mono-substituted amides ( 2- 5) derived from 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-amine were synthesized and studied by IR, 1H and 13C NMR spectroscopy. The crystal structure of 3-methyl-2,4-diphenyl-9α-(3,5-dichlorobenzamido)-3-azabicyclo[3.3.1]nonane ( 3) was determined by X-ray diffraction. NMR data showed that all compounds adopt in CDCl 3 a preferred flattened chair-chair conformation with the N-CH 3 group in equatorial disposition. X-ray data agreed with this conformation in the case of compound 3. IR data revealed that compounds 2 and 3 present a C dbnd O⋯HN intermolecular bond in the solid state. This conclusion was also confirmed by X-ray data of compound 3. In the case of compound 5, IR results suggested intermolecular NH⋯N-heterocyclic bonding. On the contrary, in the pyrazine derivative ( 4), IR, 1H and 13C NMR data showed the presence of an intramolecular NH⋯N1″-heterocyclic hydrogen bond in the solid state and solution. Moreover, NMR and IR data showed a preferred trans disposition for the NH-C dbnd O group. NMR also revealed free rotation of the -NH-CO-R group around C9-NH bond. Pharmacological assays on mice were drawn to evaluate analgesic activity.

Fabrication and testing of a newly designed slit system for depth-resolved X-ray diffraction measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sinsheimer, John; Bouet, Nathalie; Ghose, Sanjit

2016-10-06

A new system of slits called `spiderweb slits' have been developed for depth-resolved powder or polycrystalline X-ray diffraction measurements. The slits act on diffracted X-rays to select a particular gauge volume of sample, while absorbing diffracted X-rays from outside of this volume. Although the slit geometry is to some extent similar to that of previously developed conical slits or spiral slits, this new design has advantages over the previous ones in use for complex heterogeneous materials andin situandoperandodiffraction measurements. For example, the slits can measure a majority of any diffraction cone for any polycrystalline material, over a continuous range ofmore » diffraction angles, and work for X-ray energies of tens to hundreds of kiloelectronvolts. The design is generated and optimized using ray-tracing simulations, and fabricated through laser micromachining. The first prototype was successfully tested at the X17A beamline at the National Synchrotron Light Source, and shows similar performance to simulations, demonstrating gauge volume selection for standard powders, for all diffraction peaks over angles of 2–10°. A similar, but improved, design will be implemented at the X-ray Powder Diffraction beamline at the National Synchrotron Light Source II.« less

Local terahertz field enhancement for time-resolved x-ray diffraction

DOE PAGES

Kozina, M.; Pancaldi, M.; Bernhard, C.; ...

2017-02-20

We report local field strength enhancement of single-cycle terahertz (THz) pulses in an ultrafast time-resolved x-ray diffraction experiment. We show that patterning the sample with gold microstructures increases the THz field without changing the THz pulse shape or drastically affecting the quality of the x-ray diffraction pattern. Lastly, we find a five-fold increase in THz-induced x-ray diffraction intensity change in the presence of microstructures on a SrTiO 3 thin-film sample.

Local terahertz field enhancement for time-resolved x-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kozina, M.; Pancaldi, M.; Bernhard, C.

We report local field strength enhancement of single-cycle terahertz (THz) pulses in an ultrafast time-resolved x-ray diffraction experiment. We show that patterning the sample with gold microstructures increases the THz field without changing the THz pulse shape or drastically affecting the quality of the x-ray diffraction pattern. Lastly, we find a five-fold increase in THz-induced x-ray diffraction intensity change in the presence of microstructures on a SrTiO 3 thin-film sample.

Synthesis and characterization of graphene oxide using modified Hummer's method

NASA Astrophysics Data System (ADS)

Kaur, Manpreet; Kaur, Harsimran; Kukkar, Deepak

2018-05-01

In the present study, a simple approach has been followed for the synthesis of graphene oxide (GO) using modified Hummers method in which graphite powder was oxidized in the presence of concentrated H2SO4 and KMnO4. The amount of NaNO3 and KMnO4 was varied to produce sheet like structure. The varied concentrations of NaNO3 and KMnO4 resulted in yielding large amount of the product. Structural, morphological and physicochemical features of the product were studied using UV-Visible spectrophotometer, Fourier Transform infrared spectroscopy (FTIR), and crystal structure was determined using X-ray powder diffraction (XRD). UV-Vis spectra of GO was observed at a maximum absorption of 230 nm due to (π-π*) transition of atomic carbon-carbon bonds. FTIR spectra revealed the presence of oxygen containing functional groups which ensures the complete exfoliation of graphite into graphene oxide X-ray powder diffraction pattern of the product showed the diffraction peak at (2θ = 26.7°) with an interlayer spacing of 0.334 nm. All the above characterizations successfully confirmed the formation of GO.

Supramolecularly engineered perylene bisimide assemblies exhibiting thermal transition from columnar to multilamellar structures.

PubMed

Yagai, Shiki; Usui, Mari; Seki, Tomohiro; Murayama, Haruno; Kikkawa, Yoshihiro; Uemura, Shinobu; Karatsu, Takashi; Kitamura, Akihide; Asano, Atsushi; Seki, Shu

2012-05-09

Perylene 3,4:9,10-tetracarboxylic acid bisimide (PBI) was functionalized with ditopic cyanuric acid to organize it into complex columnar architectures through the formation of hydrogen-bonded supermacrocycles (rosette) by complexing with ditopic melamines possessing solubilizing alkoxyphenyl substituents. The aggregation study in solution using UV-vis and NMR spectroscopies showed the formation of extended aggregates through hydrogen-bonding and π-π stacking interactions. The cylindrical fibrillar nanostructures were visualized by microscopic techniques (AFM, TEM), and the formation of lyotropic mesophase was confirmed by polarized optical microscopy and SEM. X-ray diffraction study revealed that a well-defined hexagonal columnar (Col(h)) structure was formed by solution-casting of fibrillar assemblies. All of these results are consistent with the formation of hydrogen-bonded PBI rosettes that spontaneously organize into the Col(h) structure. Upon heating the Col(h) structure in the bulk state, a structural transition to a highly ordered lamellar (Lam) structure was observed by variable-temperature X-ray diffraction, differential scanning calorimetry, and AFM studies. IR study showed that the rearrangement of the hydrogen-bonding motifs occurs during the structural transition. These results suggest that such a striking structural transition is aided by the reorganization in the lowest level of self-organization, i.e., the rearrangement of hydrogen-bonded motifs from rosette to linear tape. A remarkable increase in the transient photoconductivity was observed by the flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements upon converting the Col(h) structure to the Lam structure. Transient absorption spectroscopy revealed that electron transfer from electron-donating alkoxyphenyl groups of melamine components to electron-deficient PBI moieties takes place, resulting in a higher probability of charge carrier generation in the Lam structure compared to the Col(h) structure.

Thermal x-ray diffraction and near-field phase contrast imaging

NASA Astrophysics Data System (ADS)

Li, Zheng; Classen, Anton; Peng, Tao; Medvedev, Nikita; Wang, Fenglin; Chapman, Henry N.; Shih, Yanhua

2017-10-01

Using higher-order coherence of thermal light sources, the resolution power of standard x-ray imaging techniques can be enhanced. In this work, we applied the higher-order measurement to far-field x-ray diffraction and near-field phase contrast imaging (PCI), in order to achieve superresolution in x-ray diffraction and obtain enhanced intensity contrast in PCI. The cost of implementing such schemes is minimal compared to the methods that achieve similar effects by using entangled x-ray photon pairs.

Thermal x-ray diffraction and near-field phase contrast imaging

DOE PAGES

Li, Zheng; Classen, Anton; Peng, Tao; ...

2017-12-27

Using higher-order coherence of thermal light sources, the resolution power of standard x-ray imaging techniques can be enhanced. Here in this work, we applied the higher-order measurement to far-field x-ray diffraction and near-field phase contrast imaging (PCI), in order to achieve superresolution in x-ray diffraction and obtain enhanced intensity contrast in PCI. The cost of implementing such schemes is minimal compared to the methods that achieve similar effects by using entangled x-ray photon pairs.

An image focusing means by using an opaque object to diffract x-rays

DOEpatents

Sommargren, Gary E.; Weaver, H. Joseph

1991-01-01

The invention provides a method and apparatus for focusing and imaging x-rays. An opaque sphere is used as a diffractive imaging element to diffract x-rays from an object so that the divergent x-ray wavefronts are transformed into convergent wavefronts and are brought to focus to form an image of the object with a large depth of field.

Soft X-Ray Diffraction Microscopy of a Frozen Hydrated Yeast Cell

DOE PAGES

Huang, Xiaojing; Nelson, Johanna; Kirz, Janos; ...

2009-11-01

We report the first image of an intact, frozen hydrated eukaryotic cell using x-ray diffraction microscopy, or coherent x-ray diffraction imaging. By plunge freezing the specimen in liquid ethane and maintaining it below -170 °C, artifacts due to dehydration, ice crystallization, and radiation damage are greatly reduced. In this example, coherent diffraction data using 520 eV x rays were recorded and reconstructed to reveal a budding yeast cell at a resolution better than 25 nm. This demonstration represents an important step towards high resolution imaging of cells in their natural, hydrated state, without limitations imposed by x-ray optics.

Difference in the structures of alanine tri- and tetra-peptides with antiparallel β-sheet assessed by X-ray diffraction, solid-state NMR and chemical shift calculations by GIPAW.

PubMed

Asakura, Tetsuo; Yazawa, Koji; Horiguchi, Kumiko; Suzuki, Furitsu; Nishiyama, Yusuke; Nishimura, Katsuyuki; Kaji, Hironori

2014-01-01

Alanine oligomers provide a key structure for silk fibers from spider and wild silkworms.We report on structural analysis of L-alanyl-L-alanyl-L-alanyl-L-alanine (Ala)4 with anti-parallel (AP) β-structures using X-ray and solid-state NMR. All of the Ala residues in the (Ala)4 are in equivalent positions, whereas for alanine trimer (Ala)3 there are two alternative locations in a unit cell as reported previously (Fawcett and Camerman, Acta Cryst., 1975, 31, 658-665). (Ala)4 with AP β-structure is more stable than AP-(Ala)3 due to formation of the stronger hydrogen bonds. The intermolecular structure of (Ala)4 is also different from polyalanine fiber structure, indicating that the interchain arrangement of AP β-structure changes with increasing alanine sequencelength. Furthermore the precise (1)H positions, which are usually inaccesible by X-ray diffraction method, are determined by high resolution (1)H solid state NMR combined with the chemical shift calculations by the gauge-including projector augmented wave method. Copyright © 2013 Wiley Periodicals, Inc.

Crystal structure, spectral property, antimicrobial activity and DFT calculation of N-(coumarin-3-yl)-N‧-(2-amino-5-phenyl-1,3,4-thiadiazol-2-yl) urea

NASA Astrophysics Data System (ADS)

Zhang, Hong-Song; Zhang, Kong-Yan; Chen, Li-Chuan; Li, Yao-Xin; Chai, Lan-Qin

2017-10-01

N-(coumarin-3-yl)-N‧-(2-amino-5-phenyl-1,3,4-thiadiazol-2-yl) urea was synthesized and characterized by elemental analysis, IR, 1H NMR, 13C NMR, UV-Vis and emission spectroscopy, as well as by single-crystal X-ray diffraction. X-ray crystallographic analyses have indicated that the crystal structure consists of two dimethyl sulfoxide (DMSO) solvent molecules and the structural geometry of DMSO is a trigonal pyramid in shape. In the crystal structure, a self-assembling two-dimensional (2-D) layer supramolecular architecture is formed through intermolecular hydrogen bonds, Cdbnd O···π (thiadiazole ring) and π···π stacking interactions. The geometry of the compound has been optimized by the DFT method and the results are compared with the X-ray diffraction data. The electronic transitions and spectral features of the compound were carried out by using DFT/B3LYP method. In addition, the antimicrobial activity was also studied, and the highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO), and HOMO-LUMO gap were also calculated.

Application of focused-beam flat-sample method to synchrotron powder X-ray diffraction with anomalous scattering effect

NASA Astrophysics Data System (ADS)

Tanaka, M.; Katsuya, Y.; Matsushita, Y.

2013-03-01

The focused-beam flat-sample method (FFM), which is a method for high-resolution and rapid synchrotron X-ray powder diffraction measurements by combination of beam focusing optics, a flat shape sample and an area detector, was applied for diffraction experiments with anomalous scattering effect. The advantages of FFM for anomalous diffraction were absorption correction without approximation, rapid data collection by an area detector and good signal-to-noise ratio data by focusing optics. In the X-ray diffraction experiments of CoFe2O4 and Fe3O4 (By FFM) using X-rays near the Fe K absorption edge, the anomalous scattering effect between Fe/Co or Fe2+/Fe3+ can be clearly detected, due to the change of diffraction intensity. The change of observed diffraction intensity as the incident X-ray energy was consistent with the calculation. The FFM is expected to be a method for anomalous powder diffraction.

Rietveld analysis using powder diffraction data with anomalous scattering effect obtained by focused beam flat sample method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tanaka, Masahiko, E-mail: masahiko@spring8.or.jp; Katsuya, Yoshio, E-mail: katsuya@spring8.or.jp; Sakata, Osami, E-mail: SAKATA.Osami@nims.go.jp

2016-07-27

Focused-beam flat-sample method (FFM) is a new trial for synchrotron powder diffraction method, which is a combination of beam focusing optics, flat shape powder sample and area detectors. The method has advantages for X-ray diffraction experiments applying anomalous scattering effect (anomalous diffraction), because of 1. Absorption correction without approximation, 2. High intensity X-rays of focused incident beams and high signal noise ratio of diffracted X-rays 3. Rapid data collection with area detectors. We applied the FFM to anomalous diffraction experiments and collected synchrotron X-ray powder diffraction data of CoFe{sub 2}O{sub 4} (inverse spinel structure) using X-rays near Fe K absorptionmore » edge, which can distinguish Co and Fe by anomalous scattering effect. We conducted Rietveld analyses with the obtained powder diffraction data and successfully determined the distribution of Co and Fe ions in CoFe{sub 2}O{sub 4} crystal structure.« less

Nontypical iodine–halogen bonds in the crystal structure of (3 E )-8-chloro-3-iodomethylidene-2,3-dihydro-1,4-oxazino[2,3,4- ij ]quinolin-4-ium triiodide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bartashevich, E. V.; Batalov, V. I.; Yushina, I. D.

2016-04-29

Two kinds of iodine–iodine halogen bonds are the focus of our attention in the crystal structure of the title salt, C 12H 8ClINO +·I 3 -, described by X-ray diffraction. The first kind is a halogen bond, reinforced by charges, between the I atom of the heterocyclic cation and the triiodide anion. The second kind is the rare case of a halogen bond between the terminal atoms of neighbouring triiodide anions. Lastly, the influence of relatively weakly bound iodine inside an asymmetric triiodide anion on the thermal and Raman spectroscopic properties has been demonstrated.

Immobilization of PMIDA on Fe3O4 magnetic nanoparticles surface: Mechanism of bonding

NASA Astrophysics Data System (ADS)

Demin, Alexander M.; Mekhaev, Alexander V.; Esin, Alexander A.; Kuznetsov, Dmitry K.; Zelenovskiy, Pavel S.; Shur, Vladimir Ya.; Krasnov, Victor P.

2018-05-01

The mechanism of N-phosphonomethyl iminodiacetic acid (PMIDA) binding with the Fe3O4 magnetic nanoparticle (MNPs) surface by Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetry was comprehensive studied. To study of microstructure, size and core structure of synthesized nanoparticles the scanning electron microscopy, X-ray diffraction analysis and Raman spectroscopy were carried out. A new scheme for the tridentate bonding of the phosphonomethyl derivative with surface Fe atoms involving unequal Psbnd Osbnd Fe bonds was proposed. The mechanism of thermal decomposition of PMIDA molecules on the MNP surface was studied using a thermogravimetric analyzer combined with infrared spectrometer. It was shown for the first time that during the thermal treatment of phosphonomethyl-modified MNPs, PMIDA molecules are not desorbed from the surface of MNPs but gradually decompose. We believe that obtained in this work data will be useful for a deeper understanding of the mechanisms of phosphonic acid derivatives interaction with MNPs, as well as in the design of new biomedical materials, in which the conjugation of biomolecules with carboxyl groups of PMIDA-modified MNPs is assumed.

Influence of micro-oxidation on joints of C/C composites and GH3044 for large-size aerospace parts

NASA Astrophysics Data System (ADS)

Shi, Xiaohong; Jin, Xiuxiu; Yan, Ningning; Yang, Li

2017-11-01

To improve the bonding strength of carbon/carbon (C/C) composites and GH3044 nickel-based superalloy, the bonding interlayer with Ti/Ni/Cu/Ni multiple foils were prepared by a two-step technique involving micro-oxidation and partial transient liquid phase (PTLP) process. Interface characteristics and mechanical behavior of joints were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), laser scanning confocal microscope (LSCM) and energy X-ray dispersive spectrometer (EDS). Results show that a porous layer on C/C composites is formed by micro-oxidation for more than 2 min at 1073 K in air, which provides a diffusion path for liquid phase to infiltrate into C/C substrate and generate a wedge interlocking interface. After micro-oxidation for 4 min, the shear strength of joints reaches 32.09 ± 1.98 MPa what is 36.73% higher than that of joints without micro-oxidation (23.47 ± 1.15 MPa). The increase of shear strength remarkably depends on physical interlocking and chemical bonding at porous interface.

Modeling the intermolecular interactions: molecular structure of N-3-hydroxyphenyl-4-methoxybenzamide.

PubMed

Karabulut, Sedat; Namli, Hilmi; Kurtaran, Raif; Yildirim, Leyla Tatar; Leszczynski, Jerzy

2014-03-01

The title compound, N-3-hydroxyphenyl-4-methoxybenzamide (3) was prepared by the acylation reaction of 3-aminophenol (1) and 4-metoxybenzoylchloride (2) in THF and characterized by ¹H NMR, ¹³C NMR and elemental analysis. Molecular structure of the crystal was determined by single crystal X-ray diffraction and DFT calculations. 3 crystallizes in monoclinic P2₁/c space group. The influence of intermolecular interactions (dimerization and crystal packing) on molecular geometry has been evaluated by calculations performed for three different models; monomer (3), dimer (4) and dimer with added unit cell contacts (5). Molecular structure of 3, 4 and 5 was optimized by applying B3LYP method with 6-31G+(d,p) basis set in gas phase and compared with X-ray crystallographic data including bond lengths, bond angles and selected dihedral angles. It has been concluded that although the crystal packing and dimerization have a minor effect on bond lengths and angles, however, these interactions are important for the dihedral angles and the rotational conformation of aromatic rings. Copyright © 2013 Elsevier Inc. All rights reserved.

Synthesis, X-ray diffraction method, spectroscopic characterization (FT-IR, 1H and 13C NMR), antimicrobial activity, Hirshfeld surface analysis and DFT computations of novel sulfonamide derivatives

NASA Astrophysics Data System (ADS)

Demircioğlu, Zeynep; Özdemir, Fethi Ahmet; Dayan, Osman; Şerbetçi, Zafer; Özdemir, Namık

2018-06-01

Synthesized compounds of N-(2-aminophenyl)benzenesulfonamide 1 and (Z)-N-(2-((2-nitrobenzylidene)amino)phenyl)benzenesulfonamide 2 were characterized by antimicrobial activity, FT-IR, 1H and 13C NMR. Two new Schiff base ligands containing aromatic sulfonamide fragment of (Z)-N-(2-((3-nitrobenzylidene)amino)phenyl)benzenesulfonamide 3 and (Z)-N-(2-((4-nitrobenzylidene)amino)phenyl)benzenesulfonamide 4 were synthesized and investigated by spectroscopic techniques including 1H and 13C NMR, FT-IR, single crystal X-ray diffraction, Hirshfeld surface, theoretical method analyses and by antimicrobial activity. The molecular geometry obtained from the X-ray structure determination was optimized Density Functional Theory (DFT/B3LYP) method with the 6-311++G(d,p) basis set in ground state. From the optimized geometry of the molecules of 3 and 4, the geometric parameters, vibrational wavenumbers and chemical shifts were computed. The optimized geometry results, which were well represented the X-ray data, were shown that the chosen of DFT/B3LYP 6-311G++(d,p) was a successful choice. After a successful optimization, frontier molecular orbitals, chemical activity, non-linear optical properties (NLO), molecular electrostatic mep (MEP), Mulliken population method, natural population analysis (NPA) and natural bond orbital analysis (NBO), which cannot be obtained experimentally, were calculated and investigated.

Pressure-induced half-collapsed-tetragonal phase in CaKFe 4 As 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaluarachchi, Udhara S.; Taufour, Valentin; Sapkota, Aashish

Here, we report the temperature-pressure phase diagram of CaKFe 4As 4 established using high-pressure electrical resistivity, magnetization, and high-energy x-ray diffraction measurements up to 6 GPa. With increasing pressure, both resistivity and magnetization data show that the bulk superconducting transition of CaKFe 4As 4 is suppressed and then disappears at p ≳ 4 GPa. High-pressure x-ray data clearly indicate a phase transition to a collapsed tetragonal phase in CaKFe 4As 4 under pressure that coincides with the abrupt loss of bulk superconductivity near 4 GPa. The x-ray data, combined with resistivity data, indicate that the collapsed tetragonal transition line ismore » essentially independent of pressure, occurring at 4.0(5) GPa for temperatures below 150 K. Density functional theory calculations also find a sudden transition to a collapsed tetragonal state near 4 GPa, as As-As bonding develops across the Ca layer. Bonding across the K layer only occurs for p ≥ 12 GPa. These findings demonstrate a different type of collapsed tetragonal phase in CaKFe 4As 4 as compared to CaFe 2As 2: a half-collapsed tetragonal phase.« less

Chalcogen analogues of nicotine lactam studied by NMR, FTIR, DFT and X-ray methods

NASA Astrophysics Data System (ADS)

Jasiewicz, Beata; Malczewska-Jaskóła, Karolina; Kowalczyk, Iwona; Warżajtis, Beata; Rychlewska, Urszula

2014-07-01

The selenoanalogue of nicotine has been synthesized and characterized by spectroscopic and X-ray diffraction methods. The crystals of selenonicotine are isomorphic with the thionicotine homologue and consist of molecules engaged in columnar π⋯π stacking interactions between antiparallely arranged pyridine moieties. These interactions, absent in other crystals containing nicotine fragments, seem to be induced by the presence of a lactam group. The molecular structures in the vacuum of the oxo-, thio- and selenonicotine homologues have been calculated by the DFT method and compared with the available X-ray data. The delocalized structure of thionicotine is stabilized by intramolecular Csbnd H⋯S hydrogen bond, which becomes weaker in the partial zwitterionic resonance structure of selenonicotine in favor of multiple Csbnd H⋯Se intermolecular hydrogen-bonds. The calculated data allow a complete assignment of vibration modes in the solid state FTIR spectra. The 1H and 13C NMR chemical shifts were calculated by the GIAO method with B3LYP/6-311G(3df) level. A comparison between experimental and calculated theoretical results indicates that the density functional B3LYP method provided satisfactory results for predicting FTIR, 1H, 13C NMR spectra properties.

Pressure-induced half-collapsed-tetragonal phase in CaKFe 4 As 4

DOE PAGES

Kaluarachchi, Udhara S.; Taufour, Valentin; Sapkota, Aashish; ...

2017-10-02

Here, we report the temperature-pressure phase diagram of CaKFe 4As 4 established using high-pressure electrical resistivity, magnetization, and high-energy x-ray diffraction measurements up to 6 GPa. With increasing pressure, both resistivity and magnetization data show that the bulk superconducting transition of CaKFe 4As 4 is suppressed and then disappears at p ≳ 4 GPa. High-pressure x-ray data clearly indicate a phase transition to a collapsed tetragonal phase in CaKFe 4As 4 under pressure that coincides with the abrupt loss of bulk superconductivity near 4 GPa. The x-ray data, combined with resistivity data, indicate that the collapsed tetragonal transition line ismore » essentially independent of pressure, occurring at 4.0(5) GPa for temperatures below 150 K. Density functional theory calculations also find a sudden transition to a collapsed tetragonal state near 4 GPa, as As-As bonding develops across the Ca layer. Bonding across the K layer only occurs for p ≥ 12 GPa. These findings demonstrate a different type of collapsed tetragonal phase in CaKFe 4As 4 as compared to CaFe 2As 2: a half-collapsed tetragonal phase.« less

Pressure-induced half-collapsed-tetragonal phase in CaKFe4As4

NASA Astrophysics Data System (ADS)

Kaluarachchi, Udhara S.; Taufour, Valentin; Sapkota, Aashish; Borisov, Vladislav; Kong, Tai; Meier, William R.; Kothapalli, Karunakar; Ueland, Benjamin G.; Kreyssig, Andreas; Valentí, Roser; McQueeney, Robert J.; Goldman, Alan I.; Bud'ko, Sergey L.; Canfield, Paul C.

2017-10-01

We report the temperature-pressure phase diagram of CaKFe4As4 established using high-pressure electrical resistivity, magnetization, and high-energy x-ray diffraction measurements up to 6 GPa. With increasing pressure, both resistivity and magnetization data show that the bulk superconducting transition of CaKFe4As4 is suppressed and then disappears at p ≳4 GPa. High-pressure x-ray data clearly indicate a phase transition to a collapsed tetragonal phase in CaKFe4As4 under pressure that coincides with the abrupt loss of bulk superconductivity near 4 GPa. The x-ray data, combined with resistivity data, indicate that the collapsed tetragonal transition line is essentially independent of pressure, occurring at 4.0(5) GPa for temperatures below 150 K. Density functional theory calculations also find a sudden transition to a collapsed tetragonal state near 4 GPa, as As-As bonding develops across the Ca layer. Bonding across the K layer only occurs for p ≥12 GPa. These findings demonstrate a different type of collapsed tetragonal phase in CaKFe4As4 as compared to CaFe2As2 : a half-collapsed tetragonal phase.

Mononuclear mercury(II) complexes containing bipyridine derivatives and thiocyanate ligands: Synthesis, characterization, crystal structure determination, and luminescent properties

NASA Astrophysics Data System (ADS)

Amani, Vahid; Alizadeh, Robabeh; Alavije, Hanieh Soleimani; Heydari, Samira Fadaei; Abafat, Marzieh

2017-08-01

A series of mercury(II) complexes, [Hg(Nsbnd N)(SCN)2] (Nsbnd N is 4,4‧-dimethyl-2,2‧-bipyridine in 1, 5,5‧-dimethyl-2,2‧-bipyridine in 2, 6,6‧-dimethyl-2,2‧-bipyridine in 3 and 6-methyl-2,2‧-bipyridine in 4), were prepared from the reactions of Hg(SCN)2 with mentioned ligands in methanol. Suitable crystals of these complexes were obtained for X-ray diffraction measurement by methanol diffusion into a DMSO solution. The four complexes were thoroughly characterized by spectral methods (IR, UV-Vis, 13C{1H}NMR, 1H NMR and luminescence), elemental analysis (CHNS) and single crystal X-ray diffraction. The X-ray structural analysis indicated that in the structures of these complexes, the mercury(II) cation is four-coordinated in a distorted tetrahedral configuration by two S atoms from two thiocyanate anions and two N atoms from one chelating 2,2‧-bipyridine derivative ligand. Also, in these complexes intermolecular interactions, for example Csbnd H⋯N hydrogen bonds (in 1-4), Csbnd H⋯S hydrogen bonds (in 1, 2 and 4), π … π interactions (in 2-4), Hg⋯N interactions (in 2) and S⋯S interactions (in 4), are effective in the stabilization of the crystal structures and the formation of the 3D supramolecular complexes. Furthermore, the luminescence spectra of the title complexes show that the intensity of their emission bands are stronger than the emission bands for the free bipyridine derivative ligands.

Investigations on Cu2+-substituted Ni-Zn ferrite nanoparticles

NASA Astrophysics Data System (ADS)

Amarjeet; Kumar, Vinod

2016-11-01

CuxNi(1-x)/2Zn(1-x)/2Fe2O4 (x = 0.1, 0.3 and 0.5) nanoparticles were prepared by chemical co-precipitation method. The developed nanoparticles were characterized for structural properties by powder X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) techniques. Peak position in the X-ray diffraction pattern confirmed the single spinel phase of the developed particles. Infrared (IR) spectroscopy in mid-IR range showed the presence of characteristic absorption bands corresponding to octahedral and tetrahedral bonds in the spinel structure of prepared samples. Thermo-gravimetric analysis (TGA) measurements showed a considerable weight loss in the developed samples above 700∘C. Frequency dependence of the electrical properties of the developed material pellets was studied in the frequency range of 1 kHz-5 MHz. Temperature dependence of the dielectric constant of Cu0.1Ni0.45Zn0.45Fe2O4 was studied at different temperatures, i.e. at 425, 450 and 475 K, in the frequency range of 1 kHz-5 MHz. It was found that the electrical conductivity decreases with increasing Cu2+ ion content while it increases with the increase in temperature.

Green synthesis of gold nanoparticles using aspartame and their catalytic activity for p-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Wu, Shufen; Yan, Songjing; Qi, Wei; Huang, Renliang; Cui, Jing; Su, Rongxin; He, Zhimin

2015-05-01

We demonstrated a facile and environmental-friendly approach to form gold nanoparticles through the reduction of HAuCl4 by aspartame. The single-crystalline structure was illustrated by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared (FTIR) results indicated that aspartame played a pivotal role in the reduction and stabilization of the gold crystals. The crystals were stabilized through the successive hydrogen-bonding network constructed between the water and aspartame molecules. Additionally, gold nanoparticles synthesized through aspartame were shown to have good catalytic activity for the reduction of p-nitrophenol to p-aminophenol in the presence of NaBH4.

Study the Synthesis, Characterization and Immersion of Dense and Porous Bovine Hydroxyapatite Structures in Hank's Balanced Salt Solution

NASA Astrophysics Data System (ADS)

Eslami, N.; Mahmoodian, R.; Hamdi, M.; Khatir, Nadia Mahmoudi; Herliansyah, M. K.; Rafieerad, Ali Reza

2017-04-01

The bone-bonding potential of biomaterials is evaluated in vitro through examining the surface apatite formation in Hank's media to enhance biocompatibility, which is also applicable to facilitate in vivo osseointegration of implantable devices. Hence, bovine hydroxyapatite (BHA) bioceramic structures have been used in various biomedical applications such as orthopedic implants. In this article, the microstructure, in vitro bioactivity, and nanomechanical properties of the synthesized dense and porous BHA are investigated via scanning electron microscopy, x-ray diffraction, energy-dispersive x-ray spectroscopy, Fourier transform infrared spectroscopy, and nanoindentation analysis. From the obtained results, porous BHA mostly possesses adequate requirements for substitution as implants in the human body.

[Effect of silicon coating on bonding strength of ceramics and titanium].

PubMed

Zhou, Shu; Wang, Yu; Zhang, Fei-Min; Guang, Han-Bing

2009-06-01

This study investigated the effect of silicon coating (SiO2) by solution-gelatin (Sol-Gel) technology on bonding strength of titanium and ceramics. Sixteen pure titanium specimens with the size of 25 mm x 3 mm x 0.5 mm were divided into two groups (n=8), test group was silicon coated by Sol-Gel technology, the other one was control group. The middle area of the samples were veneered with Vita Titankeramik system, the phase composition of two specimens were characterized by X-ray diffraction (XRD). The bonding strength of titanium/porcelain was evaluated using three-point bending test. The interface of titanium and porcelain and fractured titanium surface were investigated by scanning electron microscope (SEM) with energy depressive spectrum (EDS). Contents of surface silicon increased after modification with silicon coated by Sol-Gel technology. The mean bonding strength of test group and control group were (37.768 +/- 0.777) MPa and (29.483 +/- 1.007) MPa. There was a statistically significant difference (P=0.000) between them. The bonded ceramic boundary of test group was wider than control group. Silicon coating by Sol-Gel technology was significant in improving bonding strength of titanium/Vita Titankeramik system.

Effect of laser parameters on the microstructure of bonding porcelain layer fused on titanium

NASA Astrophysics Data System (ADS)

Chen, Xiaoyuan; Guo, Litong; Liu, Xuemei; Feng, Wei; Li, Baoe; Tao, Xueyu; Qiang, Yinghuai

2017-09-01

Bonding porcelain layer was fused on Ti surface by laser cladding process using a 400 W pulse CO2 laser. The specimens were studied by field-emission scanning electron microscopy, X-ray diffraction and bonding tests. During the laser fusion process, the porcelain powders were heated by laser energy and melted on Ti to form a chemical bond with the substrate. When the laser scanning speed decreased, the sintering temperature and the extent of the oxidation of Ti surface increased accordingly. When the laser scanning speed is 12.5 mm/s, the bonding porcelain layers were still incomplete sintered and there were some micro-cracks in the porcelain. When the laser scanning speed decreased to 7.5 mm/s, vitrified bonding porcelain layers with few pores were synthesized on Ti.

Dynamical effects in Bragg coherent x-ray diffraction imaging of finite crystals

NASA Astrophysics Data System (ADS)

Shabalin, A. G.; Yefanov, O. M.; Nosik, V. L.; Bushuev, V. A.; Vartanyants, I. A.

2017-08-01

We present simulations of Bragg coherent x-ray diffractive imaging (CXDI) data from finite crystals in the frame of the dynamical theory of x-ray diffraction. The developed approach is based on a numerical solution of modified Takagi-Taupin equations and can be applied for modeling of a broad range of x-ray diffraction experiments with finite three-dimensional crystals of arbitrary shape also in the presence of strain. We performed simulations for nanocrystals of a cubic and hemispherical shape of different sizes and provided a detailed analysis of artifacts in the Bragg CXDI reconstructions introduced by the dynamical diffraction. Based on our theoretical analysis we developed an analytical procedure to treat effects of refraction and absorption in the reconstruction. Our results elucidate limitations for the kinematical approach in the Bragg CXDI and suggest a natural criterion to distinguish between kinematical and dynamical cases in coherent x-ray diffraction on a finite crystal.

Instrument and method for X-ray diffraction, fluorescence, and crystal texture analysis without sample preparation

NASA Technical Reports Server (NTRS)

Gendreau, Keith (Inventor); Martins, Jose Vanderlei (Inventor); Arzoumanian, Zaven (Inventor)

2010-01-01

An X-ray diffraction and X-ray fluorescence instrument for analyzing samples having no sample preparation includes a X-ray source configured to output a collimated X-ray beam comprising a continuum spectrum of X-rays to a predetermined coordinate and a photon-counting X-ray imaging spectrometer disposed to receive X-rays output from an unprepared sample disposed at the predetermined coordinate upon exposure of the unprepared sample to the collimated X-ray beam. The X-ray source and the photon-counting X-ray imaging spectrometer are arranged in a reflection geometry relative to the predetermined coordinate.

Synthesis, spectra and X-ray crystallography of dipyridin-2-ylmethanone oxime and its CuX2(oxime)2 complexes: Thermal, Hirshfeld surface and DFT analysis

NASA Astrophysics Data System (ADS)

Warad, Ismail; Abdoh, Muneer; Al Ali, Anas; Shivalingegowda, Naveen; Kumara, Karthik; Zarrouk, Abdelkader; Lokanath, Neartur Krishnappagowda

2018-02-01

Dipyridin-2-ylmethanone oxime (C11H9N3O), was prepared using di-2-pyridyl ketone. The oxime ligand and its neutral CuX2 (oxime)2 (X = Cl or Br) complexes have been identified with the aid of several spectroscopic techniques such as: IR, EI-MS, EA, UV-visible, TG, 1H-NMR and finally the structure of the free oxime ligand was confirmed by X-ray diffraction studies. The oxime crystallizes in the monoclinic space group P21/c, with cell parameters a = 8.8811 (8) Å, b = 10.6362 (8) Å, c = 11.2050 (8) Å, β = 109.085 (4) º, V = 1000.26 (14) Å3 and Z = 4. The molecular conformation is stabilized by a strong intramolecular Osbnd H⋯N hydrogen bonding between the hydroxyl group of the oxime moiety and the nitrogen of the pyridine ring. Since the oxime structure was solved by XRD, the ligand structure parameters like bond length and angles were compared to the DFT computed one, the UV-visible to TD-SCF and Hirshfeld surface to MEP analysis.

Transmission Grating and Optics Technology Development for the Arcus Explorer Mission

NASA Astrophysics Data System (ADS)

Heilmann, Ralf; Arcus Team

2018-01-01

Arcus is a high-resolution x-ray spectroscopy MIDEX mission selected for a Phase A concept study. It is designed to explore structure formation through measurements of hot baryon distributions, feedback from black holes, and the formation and evolution of stars, disks, and exoplanet atmospheres. The design provides unprecedented sensitivity in the 1.2-5 nm wavelength band with effective area above 450 sqcm and spectral resolution R > 2500. The Arcus technology is based on 12 m-focal length silicon pore optics (SPO) developed for the European Athena mission, and critical-angle transmission (CAT) x-ray diffraction gratings and x-ray CCDs developed at MIT. The modular design consists of four parallel channels, each channel holding an optics petal, followed by a grating petal. CAT gratings are lightweight, alignment insensitive, high-efficiency x-ray transmission gratings that blaze into high diffraction orders, leading to high spectral resolution. Each optics petal represents an azimuthal sub-aperture of a full Wolter optic. The sub-aperturing effect increases spectral resolving power further. Two CCD readout strips receive photons from each channel, including higher-energy photons in 0th order. Each optics petal holds 34 SPO modules. Each grating petal holds 34 grating windows, and each window holds 4-6 grating facets. A grating facet consists of a silicon grating membrane, bonded to a flexure frame that interfaces with the grating window. We report on a sequence of tests with increasing complexity that systematically increase the Technology Readiness Level (TRL) for the combination of CAT gratings and SPOs towards TLR 6. CAT gratings have been evaluated in x rays for diffraction efficiency (> 30% at 2.5 nm) and for resolving power (R> 10,000). A CAT grating/SPO combination was measured at R ~ 3100 at blaze angles smaller than design values, exceeding Arcus requirements. Efficiency and resolving power were not impacted by vibration and thermal testing of gratings. A pair of large (32 mm x 32 mm) gratings was aligned using laser metrology, and alignment was verified under x rays. We present results on simultaneous illumination of the aligned grating pair, and describe our progress towards further tests.

Hydrothermal Synthesis and Characterization of a Metal-Organic Framework by Thermogravimetric Analysis, Powder X-Ray Diffraction, and Infrared Spectroscopy: An Integrative Inorganic Chemistry Experiment

ERIC Educational Resources Information Center

Crane, Johanna L.; Anderson, Kelly E.; Conway, Samantha G.

2015-01-01

This advanced undergraduate laboratory experiment involves the synthesis and characterization of a metal-organic framework with microporous channels that are held intact via hydrogen bonding of the coordinated water molecules. The hydrothermal synthesis of Co[subscript 3](BTC)[subscript 2]·12H[subscript 2]O (BTC = 1,3,5-benzene tricarboxylic acid)…

X-ray Diffraction and Density Functional Theory Provide Insight into Vanadate Binding to Homohexameric Bromoperoxidase II and the Mechanism of Bromide Oxidation.

PubMed

Radlow, Madlen; Czjzek, Mirjam; Jeudy, Alexandra; Dabin, Jerome; Delage, Ludovic; Leblanc, Catherine; Hartung, Jens

2018-05-18

X-ray diffraction of native bromoperoxidase II (EC 1.11.1.18) from the brown alga Ascophyllum nodosum reveals at a resolution of 2.26 Å details of orthovanadate binding and homohexameric protein organization. Three dimers interwoven in contact regions and tightened by hydrogen-bond-clamped guanidinium stacks along with regularly aligned water molecules form the basic structure of the enyzme. Intra- and intermolecular disulfide bridges further stabilize the enzyme preventing altogether the protein from denaturing up to a temperature of 90 °C, as evident from dynamic light scattering and the on-gel ortho-dianisidine assay. Every monomer binds one equivalent of orthovanadate in a cavity formed from side chains of three histidines, two arginines, one lysine, serine, and tryptophan. Protein binding occurs primarily through hydrogen bridges and superimposed by Coulomb attraction according to thermochemical model on density functional level of theory (B3LYP/6-311++G**). The strongest attractor is the arginine side chain mimic N-methylguanidinium, enhancing in positive cooperative manner hydrogen bridges toward weaker acceptors, such as residues from lysine and serine. Activating hydrogen peroxide occurs in the thermochemical model by side-on binding in orthovanadium peroxoic acid, oxidizing bromide with virtually no activation energy to hydrogen bonded hypobromous acid.

Philip A. Parilla | NREL

Science.gov Websites

atomic layer deposition for applications. He also manages the majority of X-ray characterization equipment at NREL, specifically X-ray diffraction and X-ray fluorescence instrumentation. Additionally, he for EERE's Hydrogen Storage program. He is also an expert in X-ray diffraction and X-ray fluorescence

Creating poly(ethylene glycol) film on the surface of NiTi alloy by gamma irradiation

NASA Astrophysics Data System (ADS)

Yu, Hongyan; Yan, Jin; Ma, Huiling; Zeng, Xinmiao; Liu, Yang; Zhao, Xinqing

2015-07-01

NiTi alloy has been extensively utilized as biomaterials owing to its unique shape memory effect, superelasticity and biocompatibility. However, concern with the toxic and allergic responses of nickel potentially releasing from implants stimulated lots of researches of modification on NiTi alloy surface. Creating chemical bond attachment of bioorganic film on NiTi alloy surface could effectively inhibit Ni releasing and obtain bioactive functions for further application. In this work, to get a bioorganic surface, NiTi alloy was modified with poly(ethylene glycol) (PEG) film by gamma ray induced grafting or crosslinking. X-ray diffraction (XRD) spectrum, water contact angle geometer and X-ray photoelectron spectroscopy (XPS) techniques were used to characterize the NiTi surface. The results indicated that PEG was covalent bonded on NiTi alloy surface. Fluorescence microscope (FM) images for morphology of 1 day osteoblast culture on the PEG coated NiTi surface showed that PEG could improve cell proliferation on NiTi surface. Our work offers a way to introduce a bioorganic metal surface by gamma irradiation.

Simulations of X-ray diffraction of shock-compressed single-crystal tantalum with synchrotron undulator sources.

PubMed

Tang, M X; Zhang, Y Y; E, J C; Luo, S N

2018-05-01

Polychromatic synchrotron undulator X-ray sources are useful for ultrafast single-crystal diffraction under shock compression. Here, simulations of X-ray diffraction of shock-compressed single-crystal tantalum with realistic undulator sources are reported, based on large-scale molecular dynamics simulations. Purely elastic deformation, elastic-plastic two-wave structure, and severe plastic deformation under different impact velocities are explored, as well as an edge release case. Transmission-mode diffraction simulations consider crystallographic orientation, loading direction, incident beam direction, X-ray spectrum bandwidth and realistic detector size. Diffraction patterns and reciprocal space nodes are obtained from atomic configurations for different loading (elastic and plastic) and detection conditions, and interpretation of the diffraction patterns is discussed.

Simulations of X-ray diffraction of shock-compressed single-crystal tantalum with synchrotron undulator sources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, M. X.; Zhang, Y. Y.; E, J. C.

Polychromatic synchrotron undulator X-ray sources are useful for ultrafast single-crystal diffraction under shock compression. Here, simulations of X-ray diffraction of shock-compressed single-crystal tantalum with realistic undulator sources are reported, based on large-scale molecular dynamics simulations. Purely elastic deformation, elastic–plastic two-wave structure, and severe plastic deformation under different impact velocities are explored, as well as an edge release case. Transmission-mode diffraction simulations consider crystallographic orientation, loading direction, incident beam direction, X-ray spectrum bandwidth and realistic detector size. Diffraction patterns and reciprocal space nodes are obtained from atomic configurations for different loading (elastic and plastic) and detection conditions, and interpretation of themore » diffraction patterns is discussed.« less

Coherent X-ray diffraction imaging of nanoengineered polymeric capsules

NASA Astrophysics Data System (ADS)

Erokhina, S.; Pastorino, L.; Di Lisa, D.; Kiiamov, A. G.; Faizullina, A. R.; Tayurskii, D. A.; Iannotta, S.; Erokhin, V.

2017-10-01

For the first time, nanoengineered polymeric capsules and their architecture have been studied with coherent X-ray diffraction imaging technique. The use of coherent X-ray diffraction imaging technique allowed us to analyze the samples immersed in a liquid. We report about the significant difference between polymeric capsule architectures under dry and liquid conditions.

A high-transparency, micro-patternable chip for X-ray diffraction analysis of microcrystals under native growth conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murray, Thomas D.; Johns Hopkins University School of Medicine, Baltimore, MD 21205; Lyubimov, Artem Y.

A highly X-ray-transparent, silicon nitride-based device has been designed and fabricated to harvest protein microcrystals for high-resolution X-ray diffraction data collection using microfocus beamlines and XFELs. Microcrystals present a significant impediment to the determination of macromolecular structures by X-ray diffraction methods. Although microfocus synchrotron beamlines and X-ray free-electron lasers (XFELs) can enable the collection of interpretable diffraction data from microcrystals, there is a need for efficient methods of harvesting small volumes (<2 µl) of microcrystals grown under common laboratory formats and delivering them to an X-ray beam source under native growth conditions. One approach that shows promise in overcoming themore » challenges intrinsic to microcrystal analysis is to pair so-called ‘fixed-target’ sample-delivery devices with microbeam-based X-ray diffraction methods. However, to record weak diffraction patterns it is necessary to fabricate devices from X-ray-transparent materials that minimize background scattering. Presented here is the design of a new micro-diffraction device consisting of three layers fabricated from silicon nitride, photoresist and polyimide film. The chip features low X-ray scattering and X-ray absorption properties, and uses a customizable blend of hydrophobic and hydrophilic surface patterns to help localize microcrystals to defined regions. Microcrystals in their native growth conditions can be loaded into the chips with a standard pipette, allowing data collection at room temperature. Diffraction data collected from hen egg-white lysozyme microcrystals (10–15 µm) loaded into the chips yielded a complete, high-resolution (<1.6 Å) data set sufficient to determine a high-quality structure by molecular replacement. The features of the chip allow the rapid and user-friendly analysis of microcrystals grown under virtually any laboratory format at microfocus synchrotron beamlines and XFELs.« less

Integrated description of protein dynamics from room-temperature X-ray crystallography and NMR

PubMed Central

Fenwick, R. Bryn; van den Bedem, Henry; Fraser, James S.; Wright, Peter E.

2014-01-01

Detailed descriptions of atomic coordinates and motions are required for an understanding of protein dynamics and their relation to molecular recognition, catalytic function, and allostery. Historically, NMR relaxation measurements have played a dominant role in the determination of the amplitudes and timescales (picosecond–nanosecond) of bond vector fluctuations, whereas high-resolution X-ray diffraction experiments can reveal the presence of and provide atomic coordinates for multiple, weakly populated substates in the protein conformational ensemble. Here we report a hybrid NMR and X-ray crystallography analysis that provides a more complete dynamic picture and a more quantitative description of the timescale and amplitude of fluctuations in atomic coordinates than is obtainable from the individual methods alone. Order parameters (S2) were calculated from single-conformer and multiconformer models fitted to room temperature and cryogenic X-ray diffraction data for dihydrofolate reductase. Backbone and side-chain order parameters derived from NMR relaxation experiments are in excellent agreement with those calculated from the room-temperature single-conformer and multiconformer models, showing that the picosecond timescale motions observed in solution occur also in the crystalline state. These motions are quenched in the crystal at cryogenic temperatures. The combination of NMR and X-ray crystallography in iterative refinement promises to provide an atomic resolution description of the alternate conformational substates that are sampled through picosecond to nanosecond timescale fluctuations of the protein structure. The method also provides insights into the structural heterogeneity of nonmethyl side chains, aromatic residues, and ligands, which are less commonly analyzed by NMR relaxation measurements. PMID:24474795

Synthesis, crystal structure, vibrational spectroscopy and photoluminescence of new hybrid compound containing chlorate anions of stanate (II)

NASA Astrophysics Data System (ADS)

Lassoued, Mohamed Saber; Abdelbaky, Mohammed S. M.; Lassoued, Abdelmajid; Meroño, Rafael Mendoza; Gadri, Abdellatif; Ammar, Salah; Ben Salah, Abdelhamid; García-Granda, Santiago

2017-08-01

The present work aimed at studying a new organic-inorganic bis (4-amino quinolinium) hexachloro stanate (II) dihydrate compound. It was prepared and characterized by single crystal X-ray diffraction, X-ray powder, Hirshfeld surface, Spectroscopy measurement, thermal study and photoluminescence properties. It was found to crystallize in the monoclinic system (P21/c space group) with the following lattice parameters: a = 7.2558(6) Å, b = 13.4876(5) Å, c = 17.2107(13) Å, β = 102.028 (12)°. Its crystal structure was determined and refined down to an R value of 0.06 and a wR value of 0.087. The structure consisted of two different alternating organic-inorganic layers. The crystal packing was stabilized by Nsbnd H⋯Cl and Osbnd H⋯Cl hydrogen bonds and π-π interactions. Hirshfeld surface analysis was used to investigate intermolecular interactions, as well 2D finger plots were conducted to reveal the contribution of these interactions in the crystal structure quantitatively. The X-ray powder is in agreement with the X-ray structure. Scanning electronic microscopy (SEM) was carried out. Furthermore, the room temperature Infra Red (IR) spectrum of the title compound was analyzed on the basis of data found in the literature. Solid state 13C NMR spectrum shows ten signals, confirming the solid state structure determined by X-ray diffraction. Thermal analysis shows two anomalies at 380 and 610 °C. The optical properties of the crystal were studied using optical absorption UV-visible and photoluminescence (PL) spectroscopy, which were investigated at room temperature.

Bobjonesite, V4+ O (SO4) (H2O 3, a new mineral species from Temple Mountain, Emery County, Utah, U.S.A

USGS Publications Warehouse

Schindler, M.; Hawthorne, F.C.; Huminicki, D.M.C.; Haynes, P.; Grice, Joel D.; Evans, H.T.

2003-01-01

Bobjonesite, V4+ O (SO4) (H2O 3, is a new mineral species from Temple Mountain, Emery County, Utah, U.S.A. It occurs as blue-green crusts and efflorescences in fractures in a fossil (Triassic) tree: individual crystals are ??1 mm and are intimately intergrown. Bobjonesite hydrates very easily, and is unstable in all but the driest atmosphere. Its structure was determined on a crystal of bobjonesite: however, the physical properties, optical properties and X-ray powder-diffraction pattern were recorded on the synthetic equivalent, and an electron-microprobe analysis was not possible. Bobjonesite has a pale blue streak, a vitreous luster and no observable fluorescence under ultraviolet light. It has no cleavage or parting. The Mohs hardness is ???1, and the calculated density is 2.28 g/cm3. Bobjonesite is biaxial positive, with ?? 1.555(2 , ?? 1.561(1), ?? 1.574(2), 2V(obs.) = 72(1)??, 2V(calc.) = 69??; it is non-pleochroic, X = b, Y ??? 19?? (in ?? obtuse). Bobjonesite is monoclinic, space group P21/n, cell dimensions from single-crystal data: a 7.3940(5), b 7.4111(3), c 12.0597(9) A??, ?? 106.55(1)??, V 633.5(1) A??3, Z=4. The strongest seven lines in the X-ray powder-diffraction pattern [d in A??(I)(hkl)] are as follows: 5.795(100)(002), 3.498(90)(112), 3.881(48)(1??03), 5.408(37) (101), 4.571(20)(012), 6.962(11 (1??01) and 6.254(11)(011). The chemical formula was derived from crystal-structure analysis; the end-member formula is V O (SO4) (H2O)3. The crystal structure of bobjonesite was refined to an R index of 3.6% for 1105 observed (Fo> 5??F) reflections measured with an automated four-circle X-ray diffractometer using MoK?? X-radiation. There is one V site occupied by V4+ and surrounded by three O atoms and three (H2O) groups in an octahedral arrangement, with one short vanadyl bond (1.577 A??), four similar equatorial bonds (<2.022 A??), and one longer V-O bond (2.278 A??) trans to the vanadyl bond. The structure consists of isolated [V4+2 O2 (H2O)6 (SO4)2] clusters linked by hydrogen bonds.

Structure determination of two structural analogs, named 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-fluorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C23H16F2N4S) and 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-chlorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C23H16ClFN4S) by synchrotron X-ray powder diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gündoğdu, Gülsüm; Aytaç, Sevim Peri; Müller, Melanie

Two novel compounds, 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-fluorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C 23H 16F 2N 4S) (1) and 3-[1-(2-fluoro-4-biphenyl)ethyl]-6-(4-chlorophenyl)-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazole (C 23H 16ClFN 4S) (2), have been designed and synthesized as cytotoxic agents. The compounds were characterized by infrared, proton nuclear magnetic resonance, mass spectral data, elemental analysis and X-ray powder diffraction. The present study comprises spectral data and crystal structures of these novel compounds determined from synchrotron X-ray powder diffraction data. The structure solutions were obtained by simulated annealing. The final structures were achieved by Rietveld refinement using soft restraints for all bond lengths, bond angles, and planar groups. Both compounds crystallize in space groupmore » $$P\\bar 1$$,Z= 2, with the unit-cell parametersa= 6.37433(9),b= 11.3641(2),c= 14.09115(19) Å,α= 80.1740(8)°,β= 85.1164(8)°,γ= 80.9831(10)°,V= 991.55(3) Å 3of compound (1) anda= 6.53736(6),b= 11.55725(15),c= 14.01373(13) Å,α= 80.3323(7)°,β= 84.8939(6)°,γ= 79.3954(8)°,V= 1024.08(2) Å 3of compound (2). Structural analyses reveal that the title compounds are isostructural.« less

Disorder effects in Mn(12)-acetate at 83 K.

PubMed

Cornia, Andrea; Fabretti, Antonio Costantino; Sessoli, Roberta; Sorace, Lorenzo; Gatteschi, Dante; Barra, Anne-Laure; Daiguebonne, Carole; Roisnel, Thierry

2002-07-01

The structure of hexadeca-mu-acetato-tetraaquadodeca-mu(3)-oxo-dodecamanganese bis(acetic acid) tetrahydrate, [Mn(12)O(12)(CH(3)COO)(16)(H(2)O)(4)] x 2CH(3)COOH x 4H(2)O, known as Mn(12)-acetate, has been determined at 83 (2) K by X-ray diffraction methods. The fourfold (S(4)) molecular symmetry is disrupted by a strong hydrogen-bonding interaction with the disordered acetic acid molecule of solvation, which displaces one of the acetate ligands in the cluster. Up to six Mn(12) isomers are potentially present in the crystal lattice, which differ in the number and arrangement of hydrogen-bonded acetic acid molecules. These results considerably improve the structural information available on this molecular nanomagnet, which was first synthesized and characterized by Lis [Acta Cryst. (1980), B36, 2042-2046].

X-Ray Structure determination of the Glycine Cleavage System Protein H of Mycobacterium tuberculosis Using An Inverse Compton Synchrotron X-Ray Source

PubMed Central

Abendroth, Jan; McCormick, Michael S.; Edwards, Thomas E.; Staker, Bart; Loewen, Roderick; Gifford, Martin; Rifkin, Jeff; Mayer, Chad; Guo, Wenjin; Zhang, Yang; Myler, Peter; Kelley, Angela; Analau, Erwin; Hewitt, Stephen Nakazawa; Napuli, Alberto J.; Kuhn, Peter; Ruth, Ronald D.; Stewart, Lance J.

2010-01-01

Structural genomics discovery projects require ready access to both X-ray and NMR instrumentation which support the collection of experimental data needed to solve large numbers of novel protein structures. The most productive X-ray crystal structure determination laboratories make extensive frequent use of tunable synchrotron X-ray light to solve novel structures by anomalous diffraction methods. This requires that frozen cryo-protected crystals be shipped to large government-run synchrotron facilities for data collection. In an effort to eliminate the need to ship crystals for data collection, we have developed the first laboratory-scale synchrotron light source capable of performing many of the state-of-the-art synchrotron applications in X-ray science. This Compact Light Source is a first-in-class device that uses inverse Compton scattering to generate X-rays of sufficient flux, tunable wavelength and beam size to allow high-resolution X-ray diffraction data collection from protein crystals. We report on benchmarking tests of X-ray diffraction data collection with hen egg white lysozyme, and the successful high-resolution X-ray structure determination of the Glycine cleavage system protein H from Mycobacterium tuberculosis using diffraction data collected with the Compact Light Source X-ray beam. PMID:20364333

Anti-contamination device for cryogenic soft X-ray diffraction microscopy

DOE PAGES

Huang, Xiaojing; Miao, Huijie; Nelson, Johanna; ...

2011-05-01

Cryogenic microscopy allows one to view frozen hydrated biological and soft matter specimens with good structural preservation and a high degree of stability against radiation damage. We describe a liquid nitrogen-cooled anti-contamination device for cryogenic X-ray diffraction microscopy. The anti-contaminator greatly reduces the buildup of ice layers on the specimen due to condensation of residual water vapor in the experimental vacuum chamber. We show by coherent X-ray diffraction measurements that this leads to fivefold reduction of background scattering, which is important for far-field X-ray diffraction microscopy of biological specimens.

Observation of electromigration in a Cu thin line by in situ coherent x-ray diffraction microscopy

NASA Astrophysics Data System (ADS)

Takahashi, Yukio; Nishino, Yoshinori; Furukawa, Hayato; Kubo, Hideto; Yamauchi, Kazuto; Ishikawa, Tetsuya; Matsubara, Eiichiro

2009-06-01

Electromigration (EM) in a 1-μm-thick Cu thin line was investigated by in situ coherent x-ray diffraction microscopy (CXDM). Characteristic x-ray speckle patterns due to both EM-induced voids and thermal deformation in the thin line were observed in the coherent x-ray diffraction patterns. Both parts of the voids and the deformation were successfully visualized in the images reconstructed from the diffraction patterns. This result not only represents the first demonstration of the visualization of structural changes in metallic materials by in situ CXDM but is also an important step toward studying the structural dynamics of nanomaterials using x-ray free-electron lasers in the near future.

Growth and characterization of barium complex of 1,3,5-triazinane-2,4,6-trione in gel: a corrosion inhibiting material

NASA Astrophysics Data System (ADS)

Divya, R.; Nair, Lekshmi P.; Bijini, B. R.; Nair, C. M. K.; Babu, K. Rajendra

2018-05-01

Good quality prismatic crystals of industrially applicable corrosion inhibiting barium complex of 1,3,5-triazinane-2,4,6-trione have been grown by conventional gel method. The crystal structure, packing, and nature of bonds are revealed in the single crystal X-ray diffraction analysis. The crystal has a three-dimensional polymeric structure having a triclinic crystal system with the space group P-1. The powder X-ray diffraction analysis confirms its crystalline nature. The functional groups present in the crystal are identified by Fourier transform infrared spectroscopy. Elemental analysis confirms the stoichiometry of the elements present in the complex. Thermogravimetric analysis and differential thermal analysis reveal its good thermal stability. The optical properties like band gap, refractive index and extinction coefficient are evaluated from the UV-visible spectral analysis. The singular property of the material, corrosion inhibition efficiency achieved by the adsorption of the sample molecules is determined by the weight loss method.

Synthesis, crystal structure, and spectral studies of 10-(2-Benzothiazolylazo)-9-phenanthrol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davydov, V. V.; Sokol, V. I.; Polyanskaya, N. A.

2012-03-15

10-(2-Benzothiazolylazo)-9-phenanthrol (L) is prepared by a reaction of 2-hydrazinobenzothiazol with 9,10-phenanthrenequinone. The crystal and molecular structure of the L{center_dot}CHCl{sub 3} solvate is determined by X-ray diffraction. The data of the X-ray diffraction study, as well as IR, {sup 1}H NMR, and electronic absorption spectra, indicate that in the crystal state and solutions the L molecule exists in the form of a quinohydrazone tautomer (b) (s-trans, cis) stabilized by the intramolecular N{sub 2}-HN{sub 2} Horizontal-Ellipsis O1 hydrogen bond. The 'mobile' H atom is located at the N2 atom of the azo group. The benzothiazolyl and phenanthrenequinone fragments are nearly coplanar. Spectroscopicmore » criteria for the state of L in various media are determined based on the data of IR, {sup 1}H NMR, and electronic absorption spectroscopy and the results of the Pariser-Parr-Pople quantum-chemical calculations.« less

Characterization of food additive-potato starch complexes by FTIR and X-ray diffraction.

PubMed

Dankar, Iman; Haddarah, Amira; Omar, Fawaz E L; Pujolà, Montserrat; Sepulcre, Francesc

2018-09-15

Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) techniques were used to study the effect of four food additives, agar, alginate, lecithin and glycerol, at three different concentrations, 0.5, 1 and 1.5%, on the molecular structure of potato puree prepared from commercial potato powder. Vibrational spectra revealed that the amylose-amylopectin skeleton present in the raw potato starch was missing in the potato powder but could be fully recovered upon water addition when the potato puree was prepared. FTIR peaks corresponding to water were clearly present in the potato powder, indicating the important structural role of water molecules in the recovery of the initial molecular conformation. None of the studied puree samples presented a crystalline structure or strong internal order. A comparison of the FTIR and XRD results revealed that the additives exerted some effects, mainly on the long-range order of the starch structure via interacting with and changing -OH and hydrogen bond interactions. Copyright © 2018 Elsevier Ltd. All rights reserved.

Beyond sixfold coordinated Si in SiO2 glass at ultrahigh pressures

PubMed Central

Prescher, Clemens; Prakapenka, Vitali B.; Stefanski, Johannes; Jahn, Sandro; Skinner, Lawrie B.; Wang, Yanbin

2017-01-01

We investigated the structure of SiO2 glass up to 172 GPa using high-energy X-ray diffraction. The combination of a multichannel collimator with diamond anvil cells enabled the measurement of structural changes in silica glass with total X-ray diffraction to previously unachievable pressures. We show that SiO2 first undergoes a change in Si–O coordination number from fourfold to sixfold between 15 and 50 GPa, in agreement with previous investigations. Above 50 GPa, the estimated coordination number continuously increases from 6 to 6.8 at 172 GPa. Si–O bond length shows first an increase due to the fourfold to sixfold coordination change and then a smaller linear decrease up to 172 GPa. We reconcile the changes in relation to the oxygen-packing fraction, showing that oxygen packing decreases at ultrahigh pressures to accommodate the higher than sixfold Si–O coordination. These results give experimental insight into the structural changes of silicate glasses as analogue materials for silicate melts at ultrahigh pressures. PMID:28874582

Beyond sixfold coordinated Si in SiO2 glass at ultrahigh pressures.

PubMed

Prescher, Clemens; Prakapenka, Vitali B; Stefanski, Johannes; Jahn, Sandro; Skinner, Lawrie B; Wang, Yanbin

2017-09-19

We investigated the structure of SiO 2 glass up to 172 GPa using high-energy X-ray diffraction. The combination of a multichannel collimator with diamond anvil cells enabled the measurement of structural changes in silica glass with total X-ray diffraction to previously unachievable pressures. We show that SiO 2 first undergoes a change in Si-O coordination number from fourfold to sixfold between 15 and 50 GPa, in agreement with previous investigations. Above 50 GPa, the estimated coordination number continuously increases from 6 to 6.8 at 172 GPa. Si-O bond length shows first an increase due to the fourfold to sixfold coordination change and then a smaller linear decrease up to 172 GPa. We reconcile the changes in relation to the oxygen-packing fraction, showing that oxygen packing decreases at ultrahigh pressures to accommodate the higher than sixfold Si-O coordination. These results give experimental insight into the structural changes of silicate glasses as analogue materials for silicate melts at ultrahigh pressures.

Hirshfeld surface analyses and crystal structures of supramolecular self-assembly thiourea derivatives directed by non-covalent interactions

NASA Astrophysics Data System (ADS)

Gumus, Ilkay; Solmaz, Ummuhan; Binzet, Gun; Keskin, Ebru; Arslan, Birdal; Arslan, Hakan

2018-04-01

The novel N-(bis(3,5-dimethoxybenzyl)carbamothioyl)-4-R-benzamide (R: H, Cl, CH3 and OCH3) compounds have been synthesized and characterized by FT-IR, 1H NMR and 13C NMR spectroscopy. Their crystal structures were also determined by single-crystal X-ray diffraction studies. Hirshfeld surfaces analysis and their associated two dimensional fingerprint plots of compounds were used as theoretical approach to assess driving force for crystal structure formation via the intermolecular interactions in the crystal lattices of synthesized compounds. The study of X-ray single crystal diffraction and Hirshfeld surfaces analysis of the prepared compounds shows that hydrogen bonding and other weaker interactions such as Nsbnd H⋯S, weak Csbnd H⋯S, Csbnd H⋯O, Csbnd H⋯N and Csbnd H···π intermolecular interactions and π-π stacking, among molecules of synthesized compounds participate in a cooperative way to stabilize the supramolecular structures.

Controllable synthesis of protein-conjugated lead sulfide nanocubes by using bovine hemoglobin as a capping agent

NASA Astrophysics Data System (ADS)

Yang, Guangrui; Qin, Dezhi; Zhang, Li

2014-06-01

A simple, convenient, and controllable strategy was reported in this contribution for protein-assisted synthesis BHb-conjugated PbS nanocubes. Powder X-ray diffraction, energy disperse X-ray spectroscopy, transmission electron microscopy, high-resolution transmission electron microscopy, and selected-area electron diffraction characterizations were used to determine the structure and morphology of BHb-conjugated PbS nanocubes. The prepared PbS nanocrystals with cubic rock salt structure were uniform and monodispersed with homogeneous size around 12 nm. The results of Fourier transform infrared and circular dichroism assay proved that Pb2+/PbS had coordination interaction with functional groups of BHb besides physical-binding effect, and the secondary structure of protein significantly changed with this interaction. Thermogravimetric analysis results confirmed the existence of BHb in PbS nanocrystals and indicated that the conjugate bonds existed between PbS and BHb. A clear perspective was shown here that special nanostructure could be created by using proteins as a mediating template at the inorganic-organic interface.

Study of solid/liquid and solid/gas interfaces in Cu-isoleucine complex by surface X-ray diffraction

NASA Astrophysics Data System (ADS)

Ferrer, Pilar; Rubio-Zuazo, Juan; Castro, German R.

2013-02-01

The enzymes could be understood like structures formed by amino acids bonded with metals, which act as active sites. The research on the coordination of metal-amino acid complexes will bring light on the behavior of metal enzymes, due to the close relation existing between the atomic structure and the functionality. The Cu-isoleucine bond is considered as a good model system to attain a better insight into the characteristics of naturally occurring copper metalloproteins. The surface structure of metal-amino acid complex could be considered as a more realistic model for real systems under biologic working conditions, since the molecular packing is decreased. In the surface, the structural constrains are reduced, keeping the structural capability of surface complex to change as a function of the surrounding environment. In this work, we present a surface X-ray diffraction study on Cu-isoleucine complex under different ambient conditions. Cu(Ile)2 crystals of about 5 mm × 5 mm × 1 mm have been growth, by seeding method in a supersaturated solution, presenting a surface of high quality. The sample for the surface diffraction study was mounted on a cell specially designed for solid/liquid or solid/gas interface analysis. The Cu-isoleucine crystal was measured under a protective dry N2 gas flow and in contact with a saturated metal amino acid solution. The bulk and the surface signals were compared, showing different atomic structures. In both cases, from surface diffraction data, it is observed that the atomic structure of the top layer undergoes a clear structural deformation. A non-uniform surface relaxation is observed producing an inhomogeneous displacement of the surface atoms towards the surface normal.

Note: application of a pixel-array area detector to simultaneous single crystal X-ray diffraction and X-ray absorption spectroscopy measurements.

PubMed

Sun, Cheng-Jun; Zhang, Bangmin; Brewe, Dale L; Chen, Jing-Sheng; Chow, G M; Venkatesan, T; Heald, Steve M

2014-04-01

X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) are two main x-ray techniques in synchrotron radiation facilities. In this Note, we present an experimental setup capable of performing simultaneous XRD and XAS measurements by the application of a pixel-array area detector. For XRD, the momentum transfer in specular diffraction was measured by scanning the X-ray energy with fixed incoming and outgoing x-ray angles. By selecting a small fixed region of the detector to collect the XRD signal, the rest of the area was available for collecting the x-ray fluorescence for XAS measurements. The simultaneous measurement of XRD and X-ray absorption near edge structure for Pr0.67Sr0.33MnO3 film was demonstrated as a proof of principle for future time-resolved pump-probe measurements. A static sample makes it easy to maintain an accurate overlap of the X-ray spot and laser pump beam.

X-Ray Diffraction Wafer Mapping Method for Rhombohedral Super-Hetero-Epitaxy

NASA Technical Reports Server (NTRS)

Park, Yoonjoon; Choi, Sang Hyouk; King, Glen C.; Elliott, James R.; Dimarcantonio, Albert L.

2010-01-01

A new X-ray diffraction (XRD) method is provided to acquire XY mapping of the distribution of single crystals, poly-crystals, and twin defects across an entire wafer of rhombohedral super-hetero-epitaxial semiconductor material. In one embodiment, the method is performed with a point or line X-ray source with an X-ray incidence angle approximating a normal angle close to 90 deg, and in which the beam mask is preferably replaced with a crossed slit. While the wafer moves in the X and Y direction, a narrowly defined X-ray source illuminates the sample and the diffracted X-ray beam is monitored by the detector at a predefined angle. Preferably, the untilted, asymmetric scans are of {440} peaks, for twin defect characterization.

Diffraction based method to reconstruct the spectrum of the Thomson scattering x-ray source

NASA Astrophysics Data System (ADS)

Chi, Zhijun; Yan, Lixin; Zhang, Zhen; Zhou, Zheng; Zheng, Lianmin; Wang, Dong; Tian, Qili; Wang, Wei; Nie, Zan; Zhang, Jie; Du, Yingchao; Hua, Jianfei; Shi, Jiaru; Pai, Chihao; Lu, Wei; Huang, Wenhui; Chen, Huaibi; Tang, Chuanxiang

2017-04-01

As Thomson scattering x-ray sources based on the collision of intense laser and relativistic electrons have drawn much attention in various scientific fields, there is an increasing demand for the effective methods to reconstruct the spectrum information of the ultra-short and high-intensity x-ray pulses. In this paper, a precise spectrum measurement method for the Thomson scattering x-ray sources was proposed with the diffraction of a Highly Oriented Pyrolytic Graphite (HOPG) crystal and was demonstrated at the Tsinghua Thomson scattering X-ray source. The x-ray pulse is diffracted by a 15 mm (L) ×15 mm (H)× 1 mm (D) HOPG crystal with 1° mosaic spread. By analyzing the diffraction pattern, both x-ray peak energies and energy spectral bandwidths at different polar angles can be reconstructed, which agree well with the theoretical value and simulation. The higher integral reflectivity of the HOPG crystal makes this method possible for single-shot measurement.

Diffraction based method to reconstruct the spectrum of the Thomson scattering x-ray source.

PubMed

Chi, Zhijun; Yan, Lixin; Zhang, Zhen; Zhou, Zheng; Zheng, Lianmin; Wang, Dong; Tian, Qili; Wang, Wei; Nie, Zan; Zhang, Jie; Du, Yingchao; Hua, Jianfei; Shi, Jiaru; Pai, Chihao; Lu, Wei; Huang, Wenhui; Chen, Huaibi; Tang, Chuanxiang

2017-04-01

As Thomson scattering x-ray sources based on the collision of intense laser and relativistic electrons have drawn much attention in various scientific fields, there is an increasing demand for the effective methods to reconstruct the spectrum information of the ultra-short and high-intensity x-ray pulses. In this paper, a precise spectrum measurement method for the Thomson scattering x-ray sources was proposed with the diffraction of a Highly Oriented Pyrolytic Graphite (HOPG) crystal and was demonstrated at the Tsinghua Thomson scattering X-ray source. The x-ray pulse is diffracted by a 15 mm (L) ×15 mm (H)× 1 mm (D) HOPG crystal with 1° mosaic spread. By analyzing the diffraction pattern, both x-ray peak energies and energy spectral bandwidths at different polar angles can be reconstructed, which agree well with the theoretical value and simulation. The higher integral reflectivity of the HOPG crystal makes this method possible for single-shot measurement.

Gas gun shock experiments with single-pulse x-ray phase contrast imaging and diffraction at the Advanced Photon Source

NASA Astrophysics Data System (ADS)

Luo, S. N.; Jensen, B. J.; Hooks, D. E.; Fezzaa, K.; Ramos, K. J.; Yeager, J. D.; Kwiatkowski, K.; Shimada, T.

2012-07-01

The highly transient nature of shock loading and pronounced microstructure effects on dynamic materials response call for in situ, temporally and spatially resolved, x-ray-based diagnostics. Third-generation synchrotron x-ray sources are advantageous for x-ray phase contrast imaging (PCI) and diffraction under dynamic loading, due to their high photon fluxes, high coherency, and high pulse repetition rates. The feasibility of bulk-scale gas gun shock experiments with dynamic x-ray PCI and diffraction measurements was investigated at the beamline 32ID-B of the Advanced Photon Source. The x-ray beam characteristics, experimental setup, x-ray diagnostics, and static and dynamic test results are described. We demonstrate ultrafast, multiframe, single-pulse PCI measurements with unprecedented temporal (<100 ps) and spatial (˜2 μm) resolutions for bulk-scale shock experiments, as well as single-pulse dynamic Laue diffraction. The results not only substantiate the potential of synchrotron-based experiments for addressing a variety of shock physics problems, but also allow us to identify the technical challenges related to image detection, x-ray source, and dynamic loading.

Effect of biaxial strain on the phase transitions of Ca ( Fe 1 – x Co x ) 2 As 2

DOE PAGES

Bohmer, A. E.; Sapkota, A.; Kreyssig, A.; ...

2017-03-10

We study the effect of applied strain as a physical control parameter for the phase transitions of Ca(Fe 1–xCo x) 2As 2 using resistivity, magnetization, x-ray diffraction, and 57Fe Mossbauer spectroscopy. Biaxial strain, namely, compression of the basal plane of the tetragonal unit cell, is created through firm bonding of samples to a rigid substrate via differential thermal expansion. This strain is shown to induce a magnetostructural phase transition in originally paramagnetic samples, and superconductivity in previously nonsuperconducting ones. Lastly, the magnetostructural transition is gradual as a consequence of using strain instead of pressure or stress as a tuning parameter.

X-ray and neutron diffraction studies of crystallinity in hydroxyapatite coatings.

PubMed

Girardin, E; Millet, P; Lodini, A

2000-02-01

To standardize industrial implant production and make comparisons between different experimental results, we have to be able to quantify the crystallinity of hydroxyapatite. Methods of measuring crystallinity ratio were developed for various HA samples before and after plasma spraying. The first series of methods uses X-ray diffraction. The advantage of these methods is that X-ray diffraction equipment is used widely in science and industry. In the second series, a neutron diffraction method is developed and the results recorded are similar to those obtained by the modified X-ray diffraction methods. The advantage of neutron diffraction is the ability to obtain measurements deep inside a component. It is a nondestructive method, owing to the very low absorption of neutrons in most materials. Copyright 2000 John Wiley & Sons, Inc.

X-ray Diffraction Gratings for Astrophysics

NASA Astrophysics Data System (ADS)

Paerels, Frits

2010-12-01

Over the past year, we have celebrated the tenth anniversary of the Chandra and XMM-Newton X-ray observatories. Both carry powerful, novel diffraction grating spectrometers, which have opened true X-ray spectroscopy for astrophysics. I will describe the design and operation of these instruments, as the background to some of the beautiful results they have produced. But these designs do not exhaust the versatility and essential simplicity of diffraction grating spectrometers, and I will discuss applications for the International X-ray Observatory IXO.

Zr doping dependence of structural and magnetic properties of cobalt ferrite synthesized by sol-gel based Pechini method

NASA Astrophysics Data System (ADS)

Motavallian, Pourya; Abasht, Behzad; Abdollah-Pour, Hassan

2018-04-01

Nanocrystalline CoZrxFe2-xO4 (0 ≤ x ≤ 0.3 in a step of 0.05) powders were synthesized by Pechini sol-gel method. The dry gel was grinded and calcined at 700 °C in a static air atmosphere for 1 h. Some tests such as thermo gravimetric analysis (TGA) combined with differential analysis (DTA), fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and vibrating sample magnetometer (VSM) were carried out to investigate the thermal behaviour, structural bonds identification, crystallographic properties, morphology and magnetic properties of the obtained powders. X-ray diffraction revealed a single-phase cubic spinel structure for all samples, where the crystallite size decreases; the lattice parameter simultaneously increases with substitution of Zr. The results of FE-SEM showed that the particle size is in the 20-70 nm range. The magnetic properties such as saturation magnetization (Ms), remanent magnetization (Mr) and coercivity (Hc) were measured from the hysteresis loops. The greatest amount of saturation magnetization for CoZr0.05Fe1.95O4 sample was 67.9 emu·g-1.

Amorphous boron gasket in diamond anvil cell research

NASA Astrophysics Data System (ADS)

Lin, Jung-Fu; Shu, Jinfu; Mao, Ho-kwang; Hemley, Russell J.; Shen, Guoyin

2003-11-01

Recent advances in high-pressure diamond anvil cell experiments include high-energy synchrotron x-ray techniques as well as new cell designs and gasketing procedures. The success of high-pressure experiments usually depends on a well-prepared sample, in which the gasket plays an important role. Various gasket materials such as diamond, beryllium, rhenium, and stainless steel have been used. Here we introduce amorphous boron as another gasket material in high-pressure diamond anvil cell experiments. We have applied the boron gasket for laser-heating x-ray diffraction, radial x-ray diffraction, nuclear resonant inelastic x-ray scattering, and inelastic x-ray scattering. The high shear strength of the amorphous boron maximizes the thickness of the sample chamber and increases the pressure homogeneity, improving the quality of high-pressure data. Use of amorphous boron avoids unwanted x-ray diffraction peaks and reduces the absorption of incident and x rays exiting the gasket material. The high quality of the diffraction patterns makes it possible to refine the cell parameters with powder x-ray diffraction data under high pressure and high temperature. The reactivity of boron prevents its use at high temperatures, however. When heated, boron may also react with the specimen to produce unwanted phases. The relatively porous boron starting material at ambient conditions also poses some challenges for sample preparation.

Preparation of TiN films by reactive high-power pulsed sputtering Penning discharges

NASA Astrophysics Data System (ADS)

Kimura, Takashi; Yoshida, Ryo; Mishima, Toshihiko; Azuma, Kingo; Nakao, Setsuo

2018-06-01

Titanium nitride (TiN) films are prepared by reactive high-power pulsed sputtering Penning discharges at a total pressure of 0.7 Pa and an average power of 60 W, where the nitrogen fraction is varied up to 15%. The peak value of the instantaneous power ranges between 3 and 14 kW, and the peak power density ranges between 0.3 and 1.2 kW cm‑2. The hardness of TiN films is higher than 22 GPa at the nitrogen fractions lower than 10% and it reaches 31 GPa at a nitrogen fraction of 5%. The X-ray diffraction peak of TiN(111) texture is observed for all prepared films, showing the grain size of about 10 nm. In X-ray photoelectron spectroscopy, oxygen is mainly bonded to titanium, but the intensity of the TiN bond is dominant in the entire Ti 2p spectrum. The intensity ratio of N 1s to Ti 2p ranges between 0.85 and 0.95.

X-Ray Sum Frequency Diffraction for Direct Imaging of Ultrafast Electron Dynamics

NASA Astrophysics Data System (ADS)

Rouxel, Jérémy R.; Kowalewski, Markus; Bennett, Kochise; Mukamel, Shaul

2018-06-01

X-ray diffraction from molecules in the ground state produces an image of their charge density, and time-resolved x-ray diffraction can thus monitor the motion of the nuclei. However, the density change of excited valence electrons upon optical excitation can barely be monitored with regular diffraction techniques due to the overwhelming background contribution of the core electrons. We present a nonlinear x-ray technique made possible by novel free electron laser sources, which provides a spatial electron density image of valence electron excitations. The technique, sum frequency generation carried out with a visible pump and a broadband x-ray diffraction pulse, yields snapshots of the transition charge densities, which represent the electron density variations upon optical excitation. The technique is illustrated by ab initio simulations of transition charge density imaging for the optically induced electronic dynamics in a donor or acceptor substituted stilbene.

X-ray diffraction and infrared spectroscopy of N,N-dimethylformamide and dimethyl sulfoxide solvatomorphs of betulonic acid.

PubMed

Boryczka, Stanisław; Jastrzebska, Maria; Bębenek, Ewa; Kusz, Joachim; Zubko, Maciej; Kadela, Monika; Michalik, Ewa

2012-12-01

X-ray diffraction and infrared spectroscopy measurements for the N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) solvatomorphs of betulonic acid (BA) were investigated. BA [3-oxolup-20(29)-en-28-oic acid, C(30)H(46)O(3)] exhibits a wide spectrum of biological activities and is considered to be a promising natural agent for the treatment of various cancer diseases. BA as a noncrystalline substance was obtained by oxidation of betulin. Crystal structures and the spectral data allowed analysis of hydrogen bonding (H-bonding), molecular conformation, and crystal packing differences in the solvatomorphs. Crystals of BA solvates were grown from the DMF-acetone (1:10, v/v) and DMSO-water (9:1, v/v) solutions. BA-DMF (1:1) solvate crystallizes in the monoclinic P2(1) space group, Z = 2. The unit cell parameters are as follows: cell lengths a = 13.2458(5) Å, b = 6.6501(2) Å, c = 17.9766(7) Å, and β = 110.513(4)°. BA-DMSO (1:1) solvate crystallizes in the orthorhombic P2(1)2(1)2(1) (Z = 4) space group with the following unit cell parameters: a = 6.6484(4) Å, b = 13.3279(8) Å, and c = 32.6821(19) Å. Conformational analysis of the six-membered rings, cyclopentane ring, and isopropenyl group showed differences in comparison with other betulin derivatives examined earlier. For both solvates, the intermolecular packing arrangement was governed mainly by H-bonds. The shortest H-bonds with D···A distances of 2.604 and 2.657 Å, and almost linear DH···A connection occurred between OH of carboxylic group of BA and oxygen atoms from O=C and O=S groups of DMF and DMSO, respectively. Copyright © 2012 Wiley Periodicals, Inc.

Molecular and crystal structure and the Hirshfeld surface analysis of 1-amino-1-deoxy-α-D-sorbopyranose and 1-amino-1-deoxy-α-D-psicopyranose ("D-sorbosamine" and "D-psicosamine") derivatives

NASA Astrophysics Data System (ADS)

Mossine, Valeri V.; Barnes, Charles L.; Mawhinney, Thomas P.

2018-05-01

Sorbosamine and psicosamine are the last two 1-amino-1-deoxy-hexuloses for which no structural data were available. We report on a13C NMR and a single crystal X-ray diffraction study of 1-deoxy-1-(N-methylphenylamino)-D-sorbose (1) and 1-deoxy-1-(N-methylphenylamino)-D-psicose (2). In solutions, both aminosugars are conformationally unstable and establish equilibria, with 90.7% α-pyranose, 3.8% α-furanose, 1.0% β-pyranose, 0.5% β-furanose, and 4.0% acyclic keto form for 1 and 32.4% α-furanose, 27.2% α-pyranose, 21.0% β-pyranose, 9.1% β-furanose, and 11.0% acyclic keto form for 2. X-ray diffraction data provided detailed structural information on 1 and 2 in the α-pyranose form. Both molecules adopt the 5C2 ring conformations, the bond distances and valence angles compare well with respective pyranose structures. All hydroxyl groups in crystal structures of both 1 and 2 participate in two-dimensional hydrogen bonding networks, the H-bonding pattern in 1 is dominated by co-crystallized water molecules. The Hirshfeld surface analysis revealed a significant contribution of non- or weakly polar interactions to the packing forces for both molecules, with crystal structure of 2 featuring short H⋯H contacts. Other structural features found in 2 are a significant planarity of the tertiary amino group (the pyramid heights are 0.127 Å in 2 vs 0.231 Å in 1), a concomitant non-involvement of the amine nitrogen in heteroatom contacts, and a unique anti-periplanar conformation around the C1sbnd C2 bond.

Hydrogen bonding in phytohormone-auxin (IAA) and its derivatives

NASA Astrophysics Data System (ADS)

Kojić-Prodić, Biserka; Kroon, Jan; Puntarec, Vitomir

1994-06-01

The significant importance of hydrogen bonds in biological structures and enzymatic reactions has been demonstrated in many examples. As a part of the molecular recognition study of auxins (plant growth hormones) the influence of hydrogen bonding on molecular conformation, particularly of the carboxyl group, which is one of the biologically active ligand sites, has been studied by X-ray diffraction and computational chemistry methods. The survey includes about 40 crystal structures of free auxins such as indol-3-ylacetic acid and its n-alkylated and halogenated derivatives but also bound auxins such as N-(indol-3-ylacetyl)- L-amino acids, and carbohydrate conjugates. The study includes hydrogen bonds of the NH⋯O and OH⋯O types. The classification of hydrogen bond patterns based on the discrimination between the centrosymmetric and non-centrosymmetric space groups and several examples of hydrogen bond systematics on graph set analysis are also shown.

Mechanical Strength and Failure Characterization of Sn-Ag-Cu Intermetallic Compound Joints at the Microscale

NASA Astrophysics Data System (ADS)

Ladani, Leila; Razmi, Jafar

2012-03-01

Continuous miniaturization of microelectronic devices has led the industry to develop interconnects on the order of a few microns for advanced superhigh-density and three-dimensional integrated circuits (3D ICs). At this scale, interconnects that conventionally consist of solder material will completely transform to intermetallic compounds (IMCs) such as Cu6Sn5. IMCs are brittle, unlike conventional solder materials that are ductile in nature; therefore, IMCs do not experience large amounts of plasticity or creep before failure. IMCs have not been fully characterized, and their mechanical and thermomechanical reliability is questioned. This study presents experimental efforts to characterize such material. Sn-based microbonds are fabricated in a controlled environment to assure complete transformation of the bonds to Cu6Sn5 IMC. Microstructural analysis including scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDS), and x-ray diffraction (XRD) is utilized to determine the IMC material composition and degree of copper diffusion into the bond area. Specimens are fabricated with different bond thicknesses and in different configurations for various tests. Normal strength of the bonds is measured utilizing double cantilever beam and peeling tests. Shear tests are conducted to quantify the shear strength of the material. Four-point bending tests are conducted to measure the fracture toughness and critical energy release rate. Bonds are fabricated in different sizes, and the size effect is investigated. The shear strength, normal strength, critical energy release rate, and effect of bond size on bond strength are reported.

Solid state and aqueous behavior of uranyl peroxide cage clusters

NASA Astrophysics Data System (ADS)

Pellegrini, Kristi Lynn

Uranyl peroxide cage clusters include a large family of more than 50 published clusters of a variety of sizes, which can incorporate various ligands including pyrophosphate and oxalate. Previous studies have reported that uranyl clusters can be used as a method to separate uranium from a solid matrix, with potential applications in reprocessing of irradiated nuclear fuel. Because of the potential applications of these novel structures in an advanced nuclear fuel cycle and their likely presence in areas of contamination, it is important to understand their behavior in both solid state and aqueous systems, including complex environments where other ions are present. In this thesis, I examine the aqueous behavior of U24Pp 12, as well as aqueous cluster systems with added mono-, di-, and trivalent cations. The resulting solutions were analyzed using dynamic light scattering and ultra-small angle X-ray scattering to evaluate the species in solution. Precipitates of these systems were analyzed using powder X-ray diffraction, X-ray fluorescence spectrometry, and Raman spectroscopy. The results of these analyses demonstrate the importance of cation size, charge, and concentration of added cations on the aqueous behavior of uranium macroions. Specifically, aggregates of various sizes and shapes form rapidly upon addition of cations, and in some cases these aggregates appear to precipitate into an X-ray amorphous material that still contains U24Pp12 clusters. In addition, I probe aggregation of U24Pp12 and U60, another uranyl peroxide cage cluster, in mixed solvent water-alcohol systems. The aggregation of uranyl clusters in water-alcohol systems is a result of hydrogen bonding with polar organic molecules and the reduction of the dielectric constant of the system. Studies of aggregation of uranyl clusters also allow for comparison between the newer uranyl polyoxometalate family and century-old transition metal polyoxometalates. To complement the solution studies of uranyl cage clusters, solid state analyses of U24Pp12 are presented, including single crystal X-ray diffraction and preliminary single crystal neutron diffraction. Solid state analyses are used to probe the complicated bonding environments between U24Pp12 and crystallized counterions, giving further insight into the importance of cluster protonation and counterions in uranyl cluster systems. The combination of solid state and solution techniques provides information about the complicated nature of uranyl peroxide nanoclusters, and insight towards future applications of clusters in the advanced nuclear fuel cycle and the environment.

Development of an adaptable coherent x-ray diffraction microscope with the emphasis on imaging hydrated specimens.

PubMed

Nam, Daewoong; Park, Jaehyun; Gallagher-Jones, Marcus; Shimada, Hiroki; Kim, Sangsoo; Kim, Sunam; Kohmura, Yoshiki; Ishikawa, Tetsuya; Song, Changyong

2013-11-01

This paper describes the development of a versatile coherent x-ray diffraction microscope capable of imaging biological specimens in solution. The microscope is a flexible platform accommodating various conditions, from low vacuum (10(-2) Pa) to helium gas filled ambient pressure. This flexibility greatly expands the application area, from in situ materials science to biology systems in their native state, by significantly relaxing restrictions to the sample environment. The coherent diffraction microscope has been used successfully to image a yeast cell immersed in buffer solution. We believe that the design of this coherent diffraction microscope can be directly adapted to various platforms such as table top soft x-ray laser, synchrotron x-ray sources, and x-ray free electron laser with minor relevant adjustments.

Development of an adaptable coherent x-ray diffraction microscope with the emphasis on imaging hydrated specimens

NASA Astrophysics Data System (ADS)

Nam, Daewoong; Park, Jaehyun; Gallagher-Jones, Marcus; Shimada, Hiroki; Kim, Sangsoo; Kim, Sunam; Kohmura, Yoshiki; Ishikawa, Tetsuya; Song, Changyong

2013-11-01

This paper describes the development of a versatile coherent x-ray diffraction microscope capable of imaging biological specimens in solution. The microscope is a flexible platform accommodating various conditions, from low vacuum (10-2 Pa) to helium gas filled ambient pressure. This flexibility greatly expands the application area, from in situ materials science to biology systems in their native state, by significantly relaxing restrictions to the sample environment. The coherent diffraction microscope has been used successfully to image a yeast cell immersed in buffer solution. We believe that the design of this coherent diffraction microscope can be directly adapted to various platforms such as table top soft x-ray laser, synchrotron x-ray sources, and x-ray free electron laser with minor relevant adjustments.

Thin Film Research. Volume 1

DTIC Science & Technology

1985-05-30

Order (FECO) ......... 23 3. X -Ray Diffraction ............................... 26 4. Transmission Electron Microscopy (TEM) ............... 26 5...remained amorphous after bombardment, as evidenced by X - ray diffraction, and showed no other changes. 0 (2) For Sb203, the crystallite size was reduced...main effect on MgF2 was the reduction in crystallite size. The films were too thir. for meaningful x - ray diffraction analysis. Durability and

X-Ray Diffraction and the Discovery of the Structure of DNA

ERIC Educational Resources Information Center

Crouse, David T.

2007-01-01

A method is described for teaching the analysis of X-ray diffraction of DNA through a series of steps utilizing the original methods used by James Watson, Francis Crick, Maurice Wilkins and Rosalind Franklin. The X-ray diffraction pattern led to the conclusion of the basic helical structure of DNA and its dimensions while basic chemical principles…

High Resolution X-Ray Diffraction of Macromolecules with Synchrotron Radiation

NASA Technical Reports Server (NTRS)

Stojanoff, Vivian; Boggon, Titus; Helliwell, John R.; Judge, Russell; Olczak, Alex; Snell, Edward H.; Siddons, D. Peter; Rose, M. Franklin (Technical Monitor)

2000-01-01

We recently combined synchrotron-based monochromatic X-ray diffraction topography methods with triple axis diffractometry and rocking curve measurements: high resolution X-ray diffraction imaging techniques, to better understand the quality of protein crystals. We discuss these methods in the light of results obtained on crystals grown under different conditions. These non destructive techniques are powerful tools in the characterization of the protein crystals and ultimately will allow to improve, develop, and understand protein crystal growth. High resolution X-ray diffraction imaging methods will be discussed in detail in light of recent results obtained on Hen Egg White Lysozyme crystals and other proteins.

Hard X-ray polarizer to enable simultaneous three-dimensional nanoscale imaging of magnetic structure and lattice strain

DOE PAGES

Logan, Jonathan; Harder, Ross; Li, Luxi; ...

2016-01-01

Recent progress in the development of dichroic Bragg coherent diffractive imaging, a new technique for simultaneous three-dimensional imaging of strain and magnetization at the nanoscale, is reported. This progress includes the installation of a diamond X-ray phase retarder at beamline 34-ID-C of the Advanced Photon Source. Here, the performance of the phase retarder for tuning X-ray polarization is demonstrated with temperature-dependent X-ray magnetic circular dichroism measurements on a gadolinium foil in transmission and on a Gd 5Si 2Ge 2crystal in diffraction geometry with a partially coherent, focused X-ray beam. Feasibility tests for dichroic Bragg coherent diffractive imaging are presented. Thesemore » tests include (1) using conventional Bragg coherent diffractive imaging to determine whether the phase retarder introduces aberrations using a nonmagnetic gold nanocrystal as a control sample, and (2) collecting coherent diffraction patterns of a magnetic Gd 5Si 2Ge 2nanocrystal with left- and right-circularly polarized X-rays. Future applications of dichroic Bragg coherent diffractive imaging for the correlation of strain and lattice defects with magnetic ordering and inhomogeneities are considered.« less

An extended N-H bond, driven by a conserved second-order interaction, orients the flavin N5 orbital in cholesterol oxidase

NASA Astrophysics Data System (ADS)

Golden, Emily; Yu, Li-Juan; Meilleur, Flora; Blakeley, Matthew P.; Duff, Anthony P.; Karton, Amir; Vrielink, Alice

2017-01-01

The protein microenvironment surrounding the flavin cofactor in flavoenzymes is key to the efficiency and diversity of reactions catalysed by this class of enzymes. X-ray diffraction structures of oxidoreductase flavoenzymes have revealed recurrent features which facilitate catalysis, such as a hydrogen bond between a main chain nitrogen atom and the flavin redox center (N5). A neutron diffraction study of cholesterol oxidase has revealed an unusual elongated main chain nitrogen to hydrogen bond distance positioning the hydrogen atom towards the flavin N5 reactive center. Investigation of the structural features which could cause such an unusual occurrence revealed a positively charged lysine side chain, conserved in other flavin mediated oxidoreductases, in a second shell away from the FAD cofactor acting to polarize the peptide bond through interaction with the carbonyl oxygen atom. Double-hybrid density functional theory calculations confirm that this electrostatic arrangement affects the N-H bond length in the region of the flavin reactive center. We propose a novel second-order partial-charge interaction network which enables the correct orientation of the hydride receiving orbital of N5. The implications of these observations for flavin mediated redox chemistry are discussed.

Exploring actinide materials through synchrotron radiation techniques.

PubMed

Shi, Wei-Qun; Yuan, Li-Yong; Wang, Cong-Zhi; Wang, Lin; Mei, Lei; Xiao, Cheng-Liang; Zhang, Li; Li, Zi-Jie; Zhao, Yu-Liang; Chai, Zhi-Fang

2014-12-10

Synchrotron radiation (SR) based techniques have been utilized with increasing frequency in the past decade to explore the brilliant and challenging sciences of actinide-based materials. This trend is partially driven by the basic needs for multi-scale actinide speciation and bonding information and also the realistic needs for nuclear energy research. In this review, recent research progresses on actinide related materials by means of various SR techniques were selectively highlighted and summarized, with the emphasis on X-ray absorption spectroscopy, X-ray diffraction and scattering spectroscopy, which are powerful tools to characterize actinide materials. In addition, advanced SR techniques for exploring future advanced nuclear fuel cycles dealing with actinides are illustrated as well. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Three Dimensional Variable-Wavelength X-Ray Bragg Coherent Diffraction Imaging

DOE PAGES

Cha, W.; Ulvestad, A.; Allain, M.; ...

2016-11-23

Here, we present and demonstrate a formalism by which three-dimensional (3D) Bragg x-ray coherent diffraction imaging (BCDI) can be implemented without moving the sample by scanning the energy of the incident x-ray beam. This capability is made possible by introducing a 3D Fourier transform that accounts for x-ray wavelength variability. We also demonstrate the approach by inverting coherent Bragg diffraction patterns from a gold nanocrystal measured with an x-ray energy scan. Furthermore, variable-wavelength BCDI will expand the breadth of feasible in situ 3D strain imaging experiments towards more diverse materials environments, especially where sample manipulation is difficult.

Synchrotron X-Ray Diffraction Analysis of Meteorites in Thin Section: Preliminary Results

NASA Technical Reports Server (NTRS)

Treiman, A. H.; Lanzirotti, A.; Xirouchakis, D.

2004-01-01

X-ray diffraction is the pre-eminent technique for mineral identification and structure determination, but is difficult to apply to grains in thin section, the standard meteorite preparation. Bright focused X-ray beams from synchrotrons have been used extensively in mineralogy and have been applied to extraterrestrial particles. The intensity and small spot size achievable in synchrotron X-ray beams makes them useful for study of materials in thin sections. Here, we describe Synchrotron X-ray Diffraction (SXRD) in thin section as done at the National Synchrotron Light Source, and cite examples of its value for studies of meteorites in thin section.

Three Dimensional Variable-Wavelength X-Ray Bragg Coherent Diffraction Imaging

NASA Astrophysics Data System (ADS)

Cha, W.; Ulvestad, A.; Allain, M.; Chamard, V.; Harder, R.; Leake, S. J.; Maser, J.; Fuoss, P. H.; Hruszkewycz, S. O.

2016-11-01

We present and demonstrate a formalism by which three-dimensional (3D) Bragg x-ray coherent diffraction imaging (BCDI) can be implemented without moving the sample by scanning the energy of the incident x-ray beam. This capability is made possible by introducing a 3D Fourier transform that accounts for x-ray wavelength variability. We demonstrate the approach by inverting coherent Bragg diffraction patterns from a gold nanocrystal measured with an x-ray energy scan. Variable-wavelength BCDI will expand the breadth of feasible in situ 3D strain imaging experiments towards more diverse materials environments, especially where sample manipulation is difficult.

Three Dimensional Variable-Wavelength X-Ray Bragg Coherent Diffraction Imaging.

PubMed

Cha, W; Ulvestad, A; Allain, M; Chamard, V; Harder, R; Leake, S J; Maser, J; Fuoss, P H; Hruszkewycz, S O

2016-11-25

We present and demonstrate a formalism by which three-dimensional (3D) Bragg x-ray coherent diffraction imaging (BCDI) can be implemented without moving the sample by scanning the energy of the incident x-ray beam. This capability is made possible by introducing a 3D Fourier transform that accounts for x-ray wavelength variability. We demonstrate the approach by inverting coherent Bragg diffraction patterns from a gold nanocrystal measured with an x-ray energy scan. Variable-wavelength BCDI will expand the breadth of feasible in situ 3D strain imaging experiments towards more diverse materials environments, especially where sample manipulation is difficult.

A new Cu–cysteamine complex: structure and optical properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Lun; Chen, Wei; Schatte, Gabriele

2014-06-07

Here we report the structure and optical properties of a new Cu–cysteamine complex (Cu–Cy) with a formula of Cu3Cl(SR)2 (R ¼ CH2CH2NH2). This Cu–Cy has a different structure from a previous Cu–Cy complex, in which both thio and amine groups from cysteamine bond with copper ions. Single-crystal X-ray diffraction and solid-state nuclear magnetic resonance results show that the oxidation state of copper in Cu3Cl(SR)2 is +1 rather than +2. Further, Cu3Cl(SR)2 has been observed to show intense photoluminescence and X-ray excited luminescence. More interesting is that Cu3Cl(SR)2 particles can produce singlet oxygen under irradiation by light or X-ray. This indicatesmore » that Cu3Cl(SR)2 is a new photosensitizer that can be used for deep cancer treatment as X-ray can penetrate soft tissues. All these findings mean that Cu3Cl(SR)2 is a new material with potential applications for lighting, radiation detection and cancer treatment.« less

In-situ X-ray diffraction system using sources and detectors at fixed angular positions

DOEpatents

Gibson, David M [Voorheesville, NY; Gibson, Walter M [Voorheesville, NY; Huang, Huapeng [Latham, NY

2007-06-26

An x-ray diffraction technique for measuring a known characteristic of a sample of a material in an in-situ state. The technique includes using an x-ray source for emitting substantially divergent x-ray radiation--with a collimating optic disposed with respect to the fixed source for producing a substantially parallel beam of x-ray radiation by receiving and redirecting the divergent paths of the divergent x-ray radiation. A first x-ray detector collects radiation diffracted from the sample; wherein the source and detector are fixed, during operation thereof, in position relative to each other and in at least one dimension relative to the sample according to a-priori knowledge about the known characteristic of the sample. A second x-ray detector may be fixed relative to the first x-ray detector according to the a-priori knowledge about the known characteristic of the sample, especially in a phase monitoring embodiment of the present invention.

The effect of exit beam phase aberrations on parallel beam coherent x-ray reconstructions

NASA Astrophysics Data System (ADS)

Hruszkewycz, S. O.; Harder, R.; Xiao, X.; Fuoss, P. H.

2010-12-01

Diffraction artifacts from imperfect x-ray windows near the sample are an important consideration in the design of coherent x-ray diffraction measurements. In this study, we used simulated and experimental diffraction patterns in two and three dimensions to explore the effect of phase imperfections in a beryllium window (such as a void or inclusion) on the convergence behavior of phasing algorithms and on the ultimate reconstruction. A predictive relationship between beam wavelength, sample size, and window position was derived to explain the dependence of reconstruction quality on beryllium defect size. Defects corresponding to this prediction cause the most damage to the sample exit wave and induce signature error oscillations during phasing that can be used as a fingerprint of experimental x-ray window artifacts. The relationship between x-ray window imperfection size and coherent x-ray diffractive imaging reconstruction quality explored in this work can play an important role in designing high-resolution in situ coherent imaging instrumentation and will help interpret the phasing behavior of coherent diffraction measured in these in situ environments.

The effect of exit beam phase aberrations on parallel beam coherent x-ray reconstructions.

PubMed

Hruszkewycz, S O; Harder, R; Xiao, X; Fuoss, P H

2010-12-01

Diffraction artifacts from imperfect x-ray windows near the sample are an important consideration in the design of coherent x-ray diffraction measurements. In this study, we used simulated and experimental diffraction patterns in two and three dimensions to explore the effect of phase imperfections in a beryllium window (such as a void or inclusion) on the convergence behavior of phasing algorithms and on the ultimate reconstruction. A predictive relationship between beam wavelength, sample size, and window position was derived to explain the dependence of reconstruction quality on beryllium defect size. Defects corresponding to this prediction cause the most damage to the sample exit wave and induce signature error oscillations during phasing that can be used as a fingerprint of experimental x-ray window artifacts. The relationship between x-ray window imperfection size and coherent x-ray diffractive imaging reconstruction quality explored in this work can play an important role in designing high-resolution in situ coherent imaging instrumentation and will help interpret the phasing behavior of coherent diffraction measured in these in situ environments.

Femtosecond X-ray Diffraction From Two-Dimensional Protein Crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frank, Matthias; Carlson, David B.; Hunter, Mark

2014-02-28

Here we present femtosecond x-ray diffraction patterns from two-dimensional (2-D) protein crystals using an x-ray free electron laser (XFEL). To date it has not been possible to acquire x-ray diffraction from individual 2-D protein crystals due to radiation damage. However, the intense and ultrafast pulses generated by an XFEL permits a new method of collecting diffraction data before the sample is destroyed. Utilizing a diffract-before-destroy methodology at the Linac Coherent Light Source, we observed Bragg diffraction to better than 8.5 Å resolution for two different 2-D protein crystal samples that were maintained at room temperature. These proof-of-principle results show promisemore » for structural analysis of both soluble and membrane proteins arranged as 2-D crystals without requiring cryogenic conditions or the formation of three-dimensional crystals.« less

Influence of gamma ray irradiation on stoichiometry of hydrothermally synthesized bismuth telluride nanoparticles

NASA Astrophysics Data System (ADS)

Abishek, N. S.; Naik, K. Gopalakrishna

2018-05-01

Bismuth telluride (Bi2Te3) nanoparticles were synthesized by the hydrothermal method at 200 °C for 24 h. The synthesized Bi2Te3 nanoparticles were irradiated with gamma rays at doses of 50 kGy and 100 kGy. The structural characterization of the pre-irradiated and post-irradiated samples was carried out by X-ray diffraction technique and was found to have rhombohedral phase having R3 ¯m (166) space group. The X-ray diffraction peaks were found to shift towards lower diffraction angle with gamma ray irradiation. The morphologies and compositions of the grown Bi2Te3 nanoparticles were studied using Field Emission Scanning Electron Microscope and X-ray energy dispersive analysis, respectively. The possible cause for the shift in the X-ray diffraction peaks with gamma ray irradiation has been discussed in the present work.

High Power Optical Coatings by Atomic Layer Deposition and Signatures of Laser-Induced Damage

DTIC Science & Technology

2012-08-28

diffraction angle 0 into crystal lattice spacing d by the Bragg condition, mX = 2d sin 0. Here X is the x - ray wavelength... angle x - ray diffraction (GAXRD) measurements, which were made at a fixed shallow incidence angle of 0.5°. Detector scans were done to measure the...was finished with 200 hafnia cycles m the fmal half period rather than 400. Crystallinity was measured by x - ray diffraction (XRD) with

Materials identification using a small-scale pixellated x-ray diffraction system

NASA Astrophysics Data System (ADS)

O'Flynn, D.; Crews, C.; Drakos, I.; Christodoulou, C.; Wilson, M. D.; Veale, M. C.; Seller, P.; Speller, R. D.

2016-05-01

A transmission x-ray diffraction system has been developed using a pixellated, energy-resolving detector (HEXITEC) and a small-scale, mains operated x-ray source (Amptek Mini-X). HEXITEC enables diffraction to be measured without the requirement of incident spectrum filtration, or collimation of the scatter from the sample, preserving a large proportion of the useful signal compared with other diffraction techniques. Due to this efficiency, sufficient molecular information for material identification can be obtained within 5 s despite the relatively low x-ray source power. Diffraction data are presented from caffeine, hexamine, paracetamol, plastic explosives and narcotics. The capability to determine molecular information from aspirin tablets inside their packaging is demonstrated. Material selectivity and the potential for a sample classification model is shown with principal component analysis, through which each different material can be clearly resolved.

Structural Characterization of β-Agostic Bonds in Pd-Catalyzed Polymerization

DOE PAGES

Xu, Hongwei; Hu, Chunhua Tony; Wang, Xiaoping; ...

2017-10-23

β-agostic Pd complexes are critical intermediates in catalytic reactions, such as olefin polymerization and Heck reactions. Pd β-agostic complexes, however, have eluded structural characterization, due to the fact that these highly unstable molecules are difficult to isolate. In this paper, we report the single-crystal X-ray and neutron diffraction characterization of β-agostic (α-diimine)Pd–ethyl intermediates in polymerization. Short C α–C β distances and acute Pd–C α–C β bond angles combined serve as unambiguous evidence for the β-agostic interaction. Finally, characterization of the agostic structure and the kinetic barrier for β-H elimination offer important insight into the fundamental understanding of agostic bonds andmore » the mechanism of polymerization.« less

Structural Characterization of β-Agostic Bonds in Pd-Catalyzed Polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Hongwei; Hu, Chunhua Tony; Wang, Xiaoping

β-agostic Pd complexes are critical intermediates in catalytic reactions, such as olefin polymerization and Heck reactions. Pd β-agostic complexes, however, have eluded structural characterization, due to the fact that these highly unstable molecules are difficult to isolate. In this paper, we report the single-crystal X-ray and neutron diffraction characterization of β-agostic (α-diimine)Pd–ethyl intermediates in polymerization. Short C α–C β distances and acute Pd–C α–C β bond angles combined serve as unambiguous evidence for the β-agostic interaction. Finally, characterization of the agostic structure and the kinetic barrier for β-H elimination offer important insight into the fundamental understanding of agostic bonds andmore » the mechanism of polymerization.« less

Direct Synthesis of Novel and Reactive Sulfide-modified Nano Iron through Nanoparticle Seeding for Improved Cadmium-Contaminated Water Treatment

PubMed Central

Su, Yiming; Adeleye, Adeyemi S.; Huang, Yuxiong; Zhou, Xuefei; Keller, Arturo A.; Zhang, Yalei

2016-01-01

Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) is of great technical and scientific interest because of its promising application in groundwater remediation, although its synthesis is still a challenge. We develop a new nanoparticle seeding method to obtain a novel and reactive nanohybrid, which contains an Fe(0) core covered by a highly sulfidized layer under high extent of sulfidation. Syntheses monitoring experiments show that seeding accelerates the reduction rate from Fe2+ to Fe0 by 19%. X-ray adsorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure analyses demonstrate the hexahedral Fe-Fe bond (2.45 and 2.83 Å) formation through breaking down of the 1.99 Å Fe-O bond both in crystalline and amorphous iron oxide. The XANES analysis also shows 24.2% (wt%) of FeS with bond length of 2.4 Å in final nanohybrid. Both X-ray diffraction and Mössbauer analyses further confirm that increased nanoparticle seeding results in formation of more Fe0 crystals. Nano-SiO2 seeding brings down the size of single Fe0 grain from 32.4 nm to 18.7 nm, enhances final Fe0 content from 5.9% to 55.6%, and increases magnetization from 4.7 to 65.5 emu/g. The synthesized nanohybrid has high cadmium removal capacity and holds promising prospects for treatment of metal-contaminated water. PMID:27095387

Direct Synthesis of Novel and Reactive Sulfide-modified Nano Iron through Nanoparticle Seeding for Improved Cadmium-Contaminated Water Treatment

NASA Astrophysics Data System (ADS)

Su, Yiming; Adeleye, Adeyemi S.; Huang, Yuxiong; Zhou, Xuefei; Keller, Arturo A.; Zhang, Yalei

2016-04-01

Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) is of great technical and scientific interest because of its promising application in groundwater remediation, although its synthesis is still a challenge. We develop a new nanoparticle seeding method to obtain a novel and reactive nanohybrid, which contains an Fe(0) core covered by a highly sulfidized layer under high extent of sulfidation. Syntheses monitoring experiments show that seeding accelerates the reduction rate from Fe2+ to Fe0 by 19%. X-ray adsorption near edge structure (XANES) spectroscopy and extended X-ray absorption fine structure analyses demonstrate the hexahedral Fe-Fe bond (2.45 and 2.83 Å) formation through breaking down of the 1.99 Å Fe-O bond both in crystalline and amorphous iron oxide. The XANES analysis also shows 24.2% (wt%) of FeS with bond length of 2.4 Å in final nanohybrid. Both X-ray diffraction and Mössbauer analyses further confirm that increased nanoparticle seeding results in formation of more Fe0 crystals. Nano-SiO2 seeding brings down the size of single Fe0 grain from 32.4 nm to 18.7 nm, enhances final Fe0 content from 5.9% to 55.6%, and increases magnetization from 4.7 to 65.5 emu/g. The synthesized nanohybrid has high cadmium removal capacity and holds promising prospects for treatment of metal-contaminated water.

Study on four polymorphs of bifendate based on X-ray crystallography.

PubMed

Nie, Jinju; Yang, Dezhi; Hu, Kun; Lu, Yang

2016-05-01

Bifendate, a synthetic anti-hepatitis drug, exhibits polycrystalline mode phenomena with 2 polymorphs reported (forms A and B). Single crystals of the known crystalline form B and 3 new crystallosolvates involving bifendate solvated with tetrahydrofuran (C), dioxane (D), and pyridine (E) in a stoichiometric ratio of 1:1 were obtained and characterized by X-ray crystallography, thermal analysis, and Fourier transform infrared (FT-IR) spectroscopy. The differences in molecular conformation, intermolecular interaction and crystal packing arrangement for the four polymorphs were determined and the basis for the polymorphisms was investigated. The rotation of single bonds resulted in different orientations for the biphenyl, methyl ester and methoxyl groups. All guest solvent molecules interacted with the host molecule via an interesting intercalative mode along the [1 0 0] direction in the channel formed by the host molecules through weak aromatic stacking interactions or non-classical hydrogen bonds, of which the volume and planarity played an important role in the intercalation of the host with the guest. The incorporation of solvent-augmented rotation of the C-C bond of the biphenyl group had a striking effect on the host molecular conformation and contributed to the formation of bifendate polymorphs. Moreover, the simulated powder X-ray diffraction (PXRD) patterns for each form were calculated on the basis of the single-crystal data and proved to be unique. The single-crystal structures of the four crystalline forms are reported in this paper.

Dynamic X-ray diffraction sampling for protein crystal positioning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scarborough, Nicole M.; Godaliyadda, G. M. Dilshan P.; Ye, Dong Hye

A sparse supervised learning approach for dynamic sampling (SLADS) is described for dose reduction in diffraction-based protein crystal positioning. Crystal centering is typically a prerequisite for macromolecular diffraction at synchrotron facilities, with X-ray diffraction mapping growing in popularity as a mechanism for localization. In X-ray raster scanning, diffraction is used to identify the crystal positions based on the detection of Bragg-like peaks in the scattering patterns; however, this additional X-ray exposure may result in detectable damage to the crystal prior to data collection. Dynamic sampling, in which preceding measurements inform the next most information-rich location to probe for image reconstruction,more » significantly reduced the X-ray dose experienced by protein crystals during positioning by diffraction raster scanning. The SLADS algorithm implemented herein is designed for single-pixel measurements and can select a new location to measure. In each step of SLADS, the algorithm selects the pixel, which, when measured, maximizes the expected reduction in distortion given previous measurements. Ground-truth diffraction data were obtained for a 5 µm-diameter beam and SLADS reconstructed the image sampling 31% of the total volume and only 9% of the interior of the crystal greatly reducing the X-ray dosage on the crystal. Furthermore, by usingin situtwo-photon-excited fluorescence microscopy measurements as a surrogate for diffraction imaging with a 1 µm-diameter beam, the SLADS algorithm enabled image reconstruction from a 7% sampling of the total volume and 12% sampling of the interior of the crystal. When implemented into the beamline at Argonne National Laboratory, without ground-truth images, an acceptable reconstruction was obtained with 3% of the image sampled and approximately 5% of the crystal. The incorporation of SLADS into X-ray diffraction acquisitions has the potential to significantly minimize the impact of X-ray exposure on the crystal by limiting the dose and area exposed for image reconstruction and crystal positioning using data collection hardware present in most macromolecular crystallography end-stations.« less

Dynamic X-ray diffraction sampling for protein crystal positioning

DOE PAGES

Scarborough, Nicole M.; Godaliyadda, G. M. Dilshan P.; Ye, Dong Hye; ...

2017-01-01

A sparse supervised learning approach for dynamic sampling (SLADS) is described for dose reduction in diffraction-based protein crystal positioning. Crystal centering is typically a prerequisite for macromolecular diffraction at synchrotron facilities, with X-ray diffraction mapping growing in popularity as a mechanism for localization. In X-ray raster scanning, diffraction is used to identify the crystal positions based on the detection of Bragg-like peaks in the scattering patterns; however, this additional X-ray exposure may result in detectable damage to the crystal prior to data collection. Dynamic sampling, in which preceding measurements inform the next most information-rich location to probe for image reconstruction,more » significantly reduced the X-ray dose experienced by protein crystals during positioning by diffraction raster scanning. The SLADS algorithm implemented herein is designed for single-pixel measurements and can select a new location to measure. In each step of SLADS, the algorithm selects the pixel, which, when measured, maximizes the expected reduction in distortion given previous measurements. Ground-truth diffraction data were obtained for a 5 µm-diameter beam and SLADS reconstructed the image sampling 31% of the total volume and only 9% of the interior of the crystal greatly reducing the X-ray dosage on the crystal. Furthermore, by usingin situtwo-photon-excited fluorescence microscopy measurements as a surrogate for diffraction imaging with a 1 µm-diameter beam, the SLADS algorithm enabled image reconstruction from a 7% sampling of the total volume and 12% sampling of the interior of the crystal. When implemented into the beamline at Argonne National Laboratory, without ground-truth images, an acceptable reconstruction was obtained with 3% of the image sampled and approximately 5% of the crystal. The incorporation of SLADS into X-ray diffraction acquisitions has the potential to significantly minimize the impact of X-ray exposure on the crystal by limiting the dose and area exposed for image reconstruction and crystal positioning using data collection hardware present in most macromolecular crystallography end-stations.« less

Dynamic X-ray diffraction sampling for protein crystal positioning

PubMed Central

Scarborough, Nicole M.; Godaliyadda, G. M. Dilshan P.; Ye, Dong Hye; Kissick, David J.; Zhang, Shijie; Newman, Justin A.; Sheedlo, Michael J.; Chowdhury, Azhad U.; Fischetti, Robert F.; Das, Chittaranjan; Buzzard, Gregery T.; Bouman, Charles A.; Simpson, Garth J.

2017-01-01

A sparse supervised learning approach for dynamic sampling (SLADS) is described for dose reduction in diffraction-based protein crystal positioning. Crystal centering is typically a prerequisite for macromolecular diffraction at synchrotron facilities, with X-ray diffraction mapping growing in popularity as a mechanism for localization. In X-ray raster scanning, diffraction is used to identify the crystal positions based on the detection of Bragg-like peaks in the scattering patterns; however, this additional X-ray exposure may result in detectable damage to the crystal prior to data collection. Dynamic sampling, in which preceding measurements inform the next most information-rich location to probe for image reconstruction, significantly reduced the X-ray dose experienced by protein crystals during positioning by diffraction raster scanning. The SLADS algorithm implemented herein is designed for single-pixel measurements and can select a new location to measure. In each step of SLADS, the algorithm selects the pixel, which, when measured, maximizes the expected reduction in distortion given previous measurements. Ground-truth diffraction data were obtained for a 5 µm-diameter beam and SLADS reconstructed the image sampling 31% of the total volume and only 9% of the interior of the crystal greatly reducing the X-ray dosage on the crystal. Using in situ two-photon-excited fluorescence microscopy measurements as a surrogate for diffraction imaging with a 1 µm-diameter beam, the SLADS algorithm enabled image reconstruction from a 7% sampling of the total volume and 12% sampling of the interior of the crystal. When implemented into the beamline at Argonne National Laboratory, without ground-truth images, an acceptable reconstruction was obtained with 3% of the image sampled and approximately 5% of the crystal. The incorporation of SLADS into X-ray diffraction acquisitions has the potential to significantly minimize the impact of X-ray exposure on the crystal by limiting the dose and area exposed for image reconstruction and crystal positioning using data collection hardware present in most macromolecular crystallography end-stations. PMID:28009558

Dynamic X-ray diffraction sampling for protein crystal positioning.

PubMed

Scarborough, Nicole M; Godaliyadda, G M Dilshan P; Ye, Dong Hye; Kissick, David J; Zhang, Shijie; Newman, Justin A; Sheedlo, Michael J; Chowdhury, Azhad U; Fischetti, Robert F; Das, Chittaranjan; Buzzard, Gregery T; Bouman, Charles A; Simpson, Garth J

2017-01-01

A sparse supervised learning approach for dynamic sampling (SLADS) is described for dose reduction in diffraction-based protein crystal positioning. Crystal centering is typically a prerequisite for macromolecular diffraction at synchrotron facilities, with X-ray diffraction mapping growing in popularity as a mechanism for localization. In X-ray raster scanning, diffraction is used to identify the crystal positions based on the detection of Bragg-like peaks in the scattering patterns; however, this additional X-ray exposure may result in detectable damage to the crystal prior to data collection. Dynamic sampling, in which preceding measurements inform the next most information-rich location to probe for image reconstruction, significantly reduced the X-ray dose experienced by protein crystals during positioning by diffraction raster scanning. The SLADS algorithm implemented herein is designed for single-pixel measurements and can select a new location to measure. In each step of SLADS, the algorithm selects the pixel, which, when measured, maximizes the expected reduction in distortion given previous measurements. Ground-truth diffraction data were obtained for a 5 µm-diameter beam and SLADS reconstructed the image sampling 31% of the total volume and only 9% of the interior of the crystal greatly reducing the X-ray dosage on the crystal. Using in situ two-photon-excited fluorescence microscopy measurements as a surrogate for diffraction imaging with a 1 µm-diameter beam, the SLADS algorithm enabled image reconstruction from a 7% sampling of the total volume and 12% sampling of the interior of the crystal. When implemented into the beamline at Argonne National Laboratory, without ground-truth images, an acceptable reconstruction was obtained with 3% of the image sampled and approximately 5% of the crystal. The incorporation of SLADS into X-ray diffraction acquisitions has the potential to significantly minimize the impact of X-ray exposure on the crystal by limiting the dose and area exposed for image reconstruction and crystal positioning using data collection hardware present in most macromolecular crystallography end-stations.

Fixture for supporting and aligning a sample to be analyzed in an x-ray diffraction apparatus

DOEpatents

Green, L.A.; Heck, J.L. Jr.

1985-04-23

A fixture is provided for supporting and aligning small samples of material on a goniometer for x-ray diffraction analysis. A sample-containing capillary is accurately positioned for rotation in the x-ray beam by selectively adjusting the fixture to position the capillary relative to the x and y axes thereof to prevent wobble and position the sample along the z axis or the axis of rotation. By employing the subject fixture relatively small samples of materials can be analyzed in an x-ray diffraction apparatus previously limited to the analysis of much larger samples.

Fixture for supporting and aligning a sample to be analyzed in an X-ray diffraction apparatus

DOEpatents

Green, Lanny A.; Heck, Jr., Joaquim L.

1987-01-01

A fixture is provided for supporting and aligning small samples of material on a goniometer for X-ray diffraction analysis. A sample-containing capillary is accurately positioned for rotation in the X-ray beam by selectively adjusting the fixture to position the capillary relative to the x and y axes thereof to prevent wobble and position the sample along the z axis or the axis of rotation. By employing the subject fixture relatively small samples of materials can be analyzed in an X-ray diffraction apparatus previously limited to the analysis of much larger samples.

Synthesis, structure and reactivity of a terminal magnesium fluoride compound, [TpBut,Me]MgF: hydrogen bonding, halogen bonding and C-F bond formation.

PubMed

Rauch, Michael; Ruccolo, Serge; Mester, John Paul; Rong, Yi; Parkin, Gerard

2016-01-01

The bulky tris(3- tert -butyl-5-pyrazolyl)hydroborato ligand, [Tp Bu t ,Me ], has been employed to obtain the first structurally characterized example of a molecular magnesium compound that features a terminal fluoride ligand, namely [Tp Bu t ,Me ]MgF, via the reaction of [Tp Bu t ,Me ]MgMe with Me 3 SnF. The chloride, bromide and iodide complexes, [Tp Bu t ,Me ]MgX (X = Cl, Br, I), can also be obtained by an analogous method using Me 3 SnX. The molecular structures of the complete series of halide derivatives, [Tp Bu t ,Me ]MgX (X = F, Cl, Br, I) have been determined by X-ray diffraction. In each case, the Mg-X bond lengths are shorter than the sum of the covalent radii, thereby indicating that there is a significant ionic component to the bonding, in agreement with density functional theory calculations. The fluoride ligand of [Tp Bu t ,Me ]MgF undergoes halide exchange with Me 3 SiX (X = Cl, Br, I) to afford [Tp Bu t ,Me ]MgX and Me 3 SiF. The other halide derivatives [Tp Bu t ,Me ]MgX undergo similar exchange reactions, but the thermodynamic driving forces are much smaller than those involving fluoride transfer, a manifestation of the often discussed silaphilicity of fluorine. In accord with the highly polarized Mg-F bond, the fluoride ligand of [Tp Bu t ,Me ]MgF is capable of serving as a hydrogen bond and halogen bond acceptor, such that it forms adducts with indole and C 6 F 5 I. [Tp Bu t ,Me ]MgF also reacts with Ph 3 CCl to afford Ph 3 CF, thereby demonstrating that [Tp Bu t ,Me ]MgF may be used to form C-F bonds.

Consequences of Optimal Bond Valence on Structural Rigidity and Improved Luminescence Properties in Sr xBa 2-xSiO 4:Eu 2+ Orthosilicate Phosphors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Denault, Kristin A.; Brgoch, Jakoah; Gaultois, Michael W.

The orthosilicate phosphors Sr xBa 2–xSiO 4:Eu 2+ have now been known for over four decades and have found extensive recent use in solid-state white lighting. It is well-recognized in the literature and in practice that intermediate compositions in the solid-solutions between the orthosilicates Sr 2SiO 4 and Ba 2SiO 4 yield the best phosphor hosts when the thermal stability of luminescence is considered. We employ a combination of synchrotron X-ray diffraction, total scattering measurements, density functional theory calculations, and low-temperature heat capacity measurements, in conjunction with detailed temperature- and time-resolved studies of luminescence properties to understand the origins ofmore » the improved luminescence properties. We observe that in the intermediate compositions, the two cation sites in the crystal structure are optimally bonded as determined from bond valence sum calculations. Optimal bonding results in a more rigid lattice, as established by the intermediate compositions possessing the highest Debye temperature, which are determined experimentally from low-temperature heat capacity measurements. Greater rigidity in turn results in the highest luminescence efficiency for intermediate compositions at elevated temperatures.« less

JMFA2—a graphically interactive Java program that fits microfibril angle X-ray diffraction data

Treesearch

Steve P. Verrill; David E. Kretschmann; Victoria L. Herian

2006-01-01

X-ray diffraction techniques have the potential to decrease the time required to determine microfibril angles dramatically. In this paper, we discuss the latest version of a curve-fitting toll that permits us to reduce the time required to evaluate MFA X-ray diffraction patterns. Further, because this tool reflects the underlying physics more accurately than existing...

Hydrogen storage properties of nano-structural carbon and metal hydrides composites

NASA Astrophysics Data System (ADS)

Miyaoka, Hiroki; Ichikawa, Takayuki; Isobe, Shigehito; Fujii, Hironobu

2006-08-01

Thermodynamic and structural properties of some ball-milled mixtures composed of the hydrogenated nanostructural carbon (C nanoH x) and metal hydride (MH; M=Li, Na, Mg and Ca) were examined from thermal desoroption mass spectroscopy and powder X-ray diffraction, respectively. The results showed that the hydrogen desorption temperatures are significantly lowered from those of each hydride (C nanoH x, MH) in the composites. This indicates that a new type of interaction exists between C nanoH x and MH, which destabilizes C-H and/or M-H bonding as well. Therefore, the above Metal-C-H system would be recognized as a new family of hydrogen storage materials.

Hydrogen bonded supra-molecular framework in inorganic-organic hybrid compounds: Syntheses, structures, and photoluminescent properties

NASA Astrophysics Data System (ADS)

Yan, Li; Liu, Wei; Li, Chuanbi; Wang, Yifei; Ma, Li; Dong, Qinqin

2013-03-01

Two novel compounds constructed from aromatic acid and N-Heterocyclic ligands have been synthesized by hydrothermal reaction: [Cd(mip)(1,8-NDC)(H2O)]2 (1) [mip = 2-(3-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline, 1,8-NDC = naphthalene-1,8-dicarboxylic acid] and Cd(mip)2(NTC)2 (2) [NTC = nicotinic acid]. Compounds 1 and 2 are characterized by elemental analysis, IR, single crystal X-ray diffraction and thermogravimetric analysis (TGA). Single-crystal X-ray investigation reveals that compounds 1-2 are 0 dimensional (0D) structures, and the existence of hydrogen bonds and π-π interactions lead the 0D to 2D novel framework. Hydrogen bonds and π-π interactions are powerful non-covalent intermolecular interactions for directing supra-molecular architectures. TG analysis shows clear courses of weight loss, which corresponds to the decomposition of different ligands. At room temperature, compound 1 exhibits emission at 449 nm upon excitation at 325 nm, and compound 2 shows a strong emission at 656 nm upon excitation at 350 nm. Fluorescent spectrum displays that compounds 1 and 2 are potential luminescent materials.

3-[4-Bromo-α( R*)-methoxybenzyl]-6-chloro-3( S*),4( S*)-dihydroxychroman: X-ray and DFT Studies

NASA Astrophysics Data System (ADS)

Sepay, Nayim; Mondal, Rina; Guha, Chayan; Mallik, Asok K.

2018-05-01

Sodium borohydride reduction of E-3-benzylidenechromanone epoxides in dry methanol has afforded 3( S*), 4( S*)-dihydroxy-3-[α( R*)-methoxybenzyl]chromans as an interesting class of products, the structures of which have been assigned mainly from spectral data and consideration of the mechanistic aspects. X-ray diffraction study of one of them, 3-[4-bromo-α( R*)-methoxybenzyl]-6-chloro-3( S*),4( S*)- dihydroxychroman, is performed. The title compound crystallizes in the monoclinic sp. gr. P21/ n, with a = 13.336(6) Å, b = 10.866(5) Å, c = 27.166(11) Å, β = 95.193(6)°, V = 3920(3) Å3, and Z = 8. Supramolecular construction of the compound involves O-H···O intermolecular hydrogen bonds as well as three other types of non-covalent interactions which are responsible for crystal packing. Density functional theory was applied for geometry optimization, molecular orbital calculations, and prediction of UV spectral features. The geometric parameters (bond lengths, bond angles, and dihedral angles) for the representative compound obtained from density functional theory with B3LY6-31G basis set were in good agreement with experimental values.

A high-transparency, micro-patternable chip for X-ray diffraction analysis of microcrystals under native growth conditions

DOE PAGES

Murray, Thomas D.; Lyubimov, Artem Y.; Ogata, Craig M.; ...

2015-08-11

Microcrystals present a significant impediment to the determination of macromolecular structures by X-ray diffraction methods. Although microfocus synchrotron beamlines and X-ray free-electron lasers (XFELs) can enable the collection of interpretable diffraction data from microcrystals, there is a need for efficient methods of harvesting small volumes (<2 µl) of microcrystals grown under common laboratory formats and delivering them to an X-ray beam source under native growth conditions. One approach that shows promise in overcoming the challenges intrinsic to microcrystal analysis is to pair so-called `fixed-target' sample-delivery devices with microbeam-based X-ray diffraction methods. However, to record weak diffraction patterns it is necessarymore » to fabricate devices from X-ray-transparent materials that minimize background scattering. Presented here is the design of a new micro-diffraction device consisting of three layers fabricated from silicon nitride, photoresist and polyimide film. The chip features low X-ray scattering and X-ray absorption properties, and uses a customizable blend of hydrophobic and hydrophilic surface patterns to help localize microcrystals to defined regions. Microcrystals in their native growth conditions can be loaded into the chips with a standard pipette, allowing data collection at room temperature. Diffraction data collected from hen egg-white lysozyme microcrystals (10–15 µm) loaded into the chips yielded a complete, high-resolution (<1.6 Å) data set sufficient to determine a high-quality structure by molecular replacement. In addition, the features of the chip allow the rapid and user-friendly analysis of microcrystals grown under virtually any laboratory format at microfocus synchrotron beamlines and XFELs.« less

A high-transparency, micro-patternable chip for X-ray diffraction analysis of microcrystals under native growth conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murray, Thomas D.; Lyubimov, Artem Y.; Ogata, Craig M.

Microcrystals present a significant impediment to the determination of macromolecular structures by X-ray diffraction methods. Although microfocus synchrotron beamlines and X-ray free-electron lasers (XFELs) can enable the collection of interpretable diffraction data from microcrystals, there is a need for efficient methods of harvesting small volumes (<2 µl) of microcrystals grown under common laboratory formats and delivering them to an X-ray beam source under native growth conditions. One approach that shows promise in overcoming the challenges intrinsic to microcrystal analysis is to pair so-called `fixed-target' sample-delivery devices with microbeam-based X-ray diffraction methods. However, to record weak diffraction patterns it is necessarymore » to fabricate devices from X-ray-transparent materials that minimize background scattering. Presented here is the design of a new micro-diffraction device consisting of three layers fabricated from silicon nitride, photoresist and polyimide film. The chip features low X-ray scattering and X-ray absorption properties, and uses a customizable blend of hydrophobic and hydrophilic surface patterns to help localize microcrystals to defined regions. Microcrystals in their native growth conditions can be loaded into the chips with a standard pipette, allowing data collection at room temperature. Diffraction data collected from hen egg-white lysozyme microcrystals (10–15 µm) loaded into the chips yielded a complete, high-resolution (<1.6 Å) data set sufficient to determine a high-quality structure by molecular replacement. In addition, the features of the chip allow the rapid and user-friendly analysis of microcrystals grown under virtually any laboratory format at microfocus synchrotron beamlines and XFELs.« less

A high-transparency, micro-patternable chip for X-ray diffraction analysis of microcrystals under native growth conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murray, Thomas D.; Lyubimov, Artem Y.; Ogata, Craig M.

Microcrystals present a significant impediment to the determination of macromolecular structures by X-ray diffraction methods. Although microfocus synchrotron beamlines and X-ray free-electron lasers (XFELs) can enable the collection of interpretable diffraction data from microcrystals, there is a need for efficient methods of harvesting small volumes (<2µl) of microcrystals grown under common laboratory formats and delivering them to an X-ray beam source under native growth conditions. One approach that shows promise in overcoming the challenges intrinsic to microcrystal analysis is to pair so-called `fixed-target' sample-delivery devices with microbeam-based X-ray diffraction methods. However, to record weak diffraction patterns it is necessary tomore » fabricate devices from X-ray-transparent materials that minimize background scattering. Presented here is the design of a new micro-diffraction device consisting of three layers fabricated from silicon nitride, photoresist and polyimide film. The chip features low X-ray scattering and X-ray absorption properties, and uses a customizable blend of hydrophobic and hydrophilic surface patterns to help localize microcrystals to defined regions. Microcrystals in their native growth conditions can be loaded into the chips with a standard pipette, allowing data collection at room temperature. Diffraction data collected from hen egg-white lysozyme microcrystals (10–15µm) loaded into the chips yielded a complete, high-resolution (<1.6Å) data set sufficient to determine a high-quality structure by molecular replacement. The features of the chip allow the rapid and user-friendly analysis of microcrystals grown under virtually any laboratory format at microfocus synchrotron beamlines and XFELs.« less

A high-transparency, micro-patternable chip for X-ray diffraction analysis of microcrystals under native growth conditions

PubMed Central

Murray, Thomas D.; Lyubimov, Artem Y.; Ogata, Craig M.; Vo, Huy; Uervirojnangkoorn, Monarin; Brunger, Axel T.; Berger, James M.

2015-01-01

Microcrystals present a significant impediment to the determination of macromolecular structures by X-ray diffraction methods. Although microfocus synchrotron beamlines and X-ray free-electron lasers (XFELs) can enable the collection of interpretable diffraction data from microcrystals, there is a need for efficient methods of harvesting small volumes (<2 µl) of microcrystals grown under common laboratory formats and delivering them to an X-ray beam source under native growth conditions. One approach that shows promise in overcoming the challenges intrinsic to microcrystal analysis is to pair so-called ‘fixed-target’ sample-delivery devices with microbeam-based X-ray diffraction methods. However, to record weak diffraction patterns it is necessary to fabricate devices from X-ray-transparent materials that minimize background scattering. Presented here is the design of a new micro-diffraction device consisting of three layers fabricated from silicon nitride, photoresist and polyimide film. The chip features low X-ray scattering and X-ray absorption properties, and uses a customizable blend of hydrophobic and hydrophilic surface patterns to help localize microcrystals to defined regions. Microcrystals in their native growth conditions can be loaded into the chips with a standard pipette, allowing data collection at room temperature. Diffraction data collected from hen egg-white lysozyme microcrystals (10–15 µm) loaded into the chips yielded a complete, high-resolution (<1.6 Å) data set sufficient to determine a high-quality structure by molecular replacement. The features of the chip allow the rapid and user-friendly analysis of microcrystals grown under virtually any laboratory format at microfocus synchrotron beamlines and XFELs. PMID:26457423

Solid state structural investigations of the bis(chalcone) compound with single crystal X-ray crystallography, DFT, gamma-ray spectroscopy and chemical spectroscopy methods

NASA Astrophysics Data System (ADS)

Yakalı, Gül; Biçer, Abdullah; Eke, Canel; Cin, Günseli Turgut

2018-04-01

A bis(chalcone), (2E,6E)-2,6-bis((E)-3phenylallidene)cyclohexanone, was characterized by 1H NMR, 13C NMR, FTIR, UV-Vis spectroscopy, gamma-ray spectroscopy and single crystal X- ray structural analysis. The optimized molecular structure of the compound is calculated using DFT/B3LYP with 6-31G (d,p) level. The calculated geometrical parameters are in good agreement with the experimental data obtained from our reported X-ray structure. The powder and single crystal compounds were gama-irradiated using clinical electron linear accelerator and 60Co gamma-ray source, respectively. Spectral studies (1H NMR, 13C NMR, FTIR and UV-Vis) of powder chalcone compound were also investigated before and after irradiation. Depending on the irradiation notable changes were observed in spectral features powder sample. Single crystal X-ray diffraction investigation shows that both unirradiated and irradiated single crystal samples crystallizes in a orthorhombic crystal system in the centrosymmetric space group Pbcn and exhibits an C-H..O intramolecular and intermolecular hydrogen bonds. The crystal packing is stabilised by strong intermolecular bifurcate C-H..O hydrogen bonds and π…π stacking interactions. The asymmetric unit of the title compound contains one-half of a molecule. The other half of the molecule is generated with (1-x,y,-3/2-z) symmetry operator. The molecule is almost planar due to having π conjugated system of chalcones. However, irradiated single crystal compound showed significant changes lattice parameters, crystal volume and density. According to results of gamma-ray spectroscopy, radioactive elements of powder compound which are 123Sb(n,g),124Sb,57Fe(g,p),56Mn, 55Mn(g,n), and 54Mn were determined using photoactivation analysis. However, the most intensive gamma-ray energy signals are 124Sb.

XPS Spectra Analysis of Ti2+, Ti3+ Ions and Dye Photodegradation Evaluation of Titania-Silica Mixed Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Chinh, Vu Duc; Broggi, Alessandra; Di Palma, Luca; Scarsella, Marco; Speranza, Giorgio; Vilardi, Giorgio; Thang, Pham Nam

2018-04-01

TiO2-SiO2 mixed oxides have been prepared by the sol-gel technique from tetrabutyl orthotitanate and tetraethyl orthosilicate. The prepared materials were characterized by x-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectroscopy, nitrogen physisorption, Fourier-transform infrared spectroscopy (FT-IR) and x-ray photoelectron spectroscopy (XPS). The results indicate that the TiO2-SiO2 mixed oxides have a large surface area and a nanoscale size. FT-IR spectra show that Ti atoms are bonded to silica by oxygen bridging atoms in Ti-O-Si bonds. The titanium valence states in TiO2-SiO2 mixed oxides were investigated by XPS, and their spectra report the presence of Ti2+ and Ti3+ cations for high silica concentration, suggesting the formation of oxygen vacancies. The photocatalytic activity of the prepared materials has been evaluated for the photodegradation of methylene blue (MB). The mixed oxides were activated by means of a UV light source, and the concentration of MB was monitored by UV-Vis spectroscopy. The synthesized TiO2-SiO2 shows significantly higher MB removal efficiency in comparison with that of the commercial TiO2 Degussa, P25.

Morphological, chemical and structural characterisation of deciduous enamel: SEM, EDS, XRD, FTIR and XPS analysis.

PubMed

Zamudio-Ortega, C M; Contreras-Bulnes, R; Scougall-Vilchis, R J; Morales-Luckie, R A; Olea-Mejía, O F; Rodríguez-Vilchis, L E

2014-09-01

The purpose of this study was to characterise the enamel surface of sound deciduous teeth in terms of morphology, chemical composition, structure and crystalline phases. The enamel of 30 human deciduous teeth was examined by: Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray Spectroscopy (EDS), X-ray Powder Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and X-ray Photoelectron Spectroscopy (XPS). Chemical differences between incisors and canines were statistically evaluated using the Mann-Whitney U test (p ≤ 0.05). Three enamel patterns were observed by SEM: 'mostly smooth with some groves', 'abundant microporosities' and 'exposed prisms'. The average Ca/P molar ratios were 1.37 and 1.03 by EDS and XPS, respectively. The crystallite size determined by XRD was 210.82 ± 16.78 Å. The mean ratio between Ca bonded to phosphate and Ca bonded to hydroxyl was approximately 10:1. The enamel of sound deciduous teeth showed two main patterns: 'mostly smooth with some groves' and 'abundant microporosities'. 'Exposed prisms' was a secondary pattern. There were slight variations among the Ca/P molar ratios found by EDS and XPS, suggesting differences in the mineral content from the enamel surface to the interior. The crystalline phases found in enamel were hydroxyapatite and carbonate apatite, with major type B than type A carbonate incorporation.

A new Pu(iii) coordination geometry in (C5H5NBr)2[PuCl3(H2O)5]·2Cl·2H2O as obtained via supramolecular assembly in aqueous, high chloride media.

PubMed

Surbella, Robert G; Ducati, Lucas C; Pellegrini, Kristi L; McNamara, Bruce K; Autschbach, Jochen; Schwantes, Jon M; Cahill, Christopher L

2017-09-28

Crystals of a hydrated Pu(iii) chloride, (C 5 H 5 NBr) 2 [PuCl 3 (H 2 O) 5 ]·2Cl·2H 2 O, were grown via slow evaporation from acidic aqueous, high chloride media. X-ray diffraction data reveals the neutral [PuCl 3 (H 2 O) 5 ] tecton is assembled via charge assisted hydrogen and halogen bonds donated by 4-bromopyridinium cations and a series of inter-tecton hydrogen bonds.

Interactions between graphene oxide and wide band gap semiconductors

NASA Astrophysics Data System (ADS)

Kawa, M.; Podborska, A.; Szaciłowski, K.

2016-09-01

The graphene oxide (GO) and GO@TiO2 nanocomposite have been synthesised by using modified Hummers method and ultrasonics respectively. The materials were characterized by using X-ray diffraction, Fourier transform infrared spectroscopy and UV-Vis absorption spectroscopy. It was found that the interaction between GO and TiO2 affects the average interlayer spacing in carbonaceous material. The formation of bonds between various oxygen-containing functional groups and surface of titanium dioxide was investigated. One of them formed between the quinone structures (occur in graphene oxide) and titanium atoms exhibited 1.5 bond order. Furthermore the charge-transfer processes in GO@TiO2 composite were observed.

High-resolution x-ray diffraction microscopy of specifically labeled yeast cells

PubMed Central

Nelson, Johanna; Huang, Xiaojing; Steinbrener, Jan; Shapiro, David; Kirz, Janos; Marchesini, Stefano; Neiman, Aaron M.; Turner, Joshua J.; Jacobsen, Chris

2010-01-01

X-ray diffraction microscopy complements other x-ray microscopy methods by being free of lens-imposed radiation dose and resolution limits, and it allows for high-resolution imaging of biological specimens too thick to be viewed by electron microscopy. We report here the highest resolution (11–13 nm) x-ray diffraction micrograph of biological specimens, and a demonstration of molecular-specific gold labeling at different depths within cells via through-focus propagation of the reconstructed wavefield. The lectin concanavalin A conjugated to colloidal gold particles was used to label the α-mannan sugar in the cell wall of the yeast Saccharomyces cerevisiae. Cells were plunge-frozen in liquid ethane and freeze-dried, after which they were imaged whole using x-ray diffraction microscopy at 750 eV photon energy. PMID:20368463

High-resolution x-ray diffraction microscopy of specifically labeled yeast cells

DOE PAGES

Nelson, Johanna; Huang, Xiaojing; Steinbrener, Jan; ...

2010-04-20

X-ray diffraction microscopy complements other x-ray microscopy methods by being free of lens-imposed radiation dose and resolution limits, and it allows for high-resolution imaging of biological specimens too thick to be viewed by electron microscopy. We report here the highest resolution (11-13 nm) x-ray diffraction micrograph of biological specimens, and a demonstration of molecular-specific gold labeling at different depths within cells via through-focus propagation of the reconstructed wavefield. The lectin concanavalin A conjugated to colloidal gold particles was used to label the α-mannan sugar in the cell wall of the yeast Saccharomyces cerevisiae. Cells were plunge-frozen in liquid ethane andmore » freeze-dried, after which they were imaged whole using x-ray diffraction microscopy at 750 eV photon energy.« less

Sub-atomic resolution X-ray crystallography and neutron crystallography: promise, challenges and potential.

PubMed

Blakeley, Matthew P; Hasnain, Samar S; Antonyuk, Svetlana V

2015-07-01

The International Year of Crystallography saw the number of macromolecular structures deposited in the Protein Data Bank cross the 100000 mark, with more than 90000 of these provided by X-ray crystallography. The number of X-ray structures determined to sub-atomic resolution (i.e. ≤1 Å) has passed 600 and this is likely to continue to grow rapidly with diffraction-limited synchrotron radiation sources such as MAX-IV (Sweden) and Sirius (Brazil) under construction. A dozen X-ray structures have been deposited to ultra-high resolution (i.e. ≤0.7 Å), for which precise electron density can be exploited to obtain charge density and provide information on the bonding character of catalytic or electron transfer sites. Although the development of neutron macromolecular crystallography over the years has been far less pronounced, and its application much less widespread, the availability of new and improved instrumentation, combined with dedicated deuteration facilities, are beginning to transform the field. Of the 83 macromolecular structures deposited with neutron diffraction data, more than half (49/83, 59%) were released since 2010. Sub-mm(3) crystals are now regularly being used for data collection, structures have been determined to atomic resolution for a few small proteins, and much larger unit-cell systems (cell edges >100 Å) are being successfully studied. While some details relating to H-atom positions are tractable with X-ray crystallography at sub-atomic resolution, the mobility of certain H atoms precludes them from being located. In addition, highly polarized H atoms and protons (H(+)) remain invisible with X-rays. Moreover, the majority of X-ray structures are determined from cryo-cooled crystals at 100 K, and, although radiation damage can be strongly controlled, especially since the advent of shutterless fast detectors, and by using limited doses and crystal translation at micro-focus beams, radiation damage can still take place. Neutron crystallography therefore remains the only approach where diffraction data can be collected at room temperature without radiation damage issues and the only approach to locate mobile or highly polarized H atoms and protons. Here a review of the current status of sub-atomic X-ray and neutron macromolecular crystallography is given and future prospects for combined approaches are outlined. New results from two metalloproteins, copper nitrite reductase and cytochrome c', are also included, which illustrate the type of information that can be obtained from sub-atomic-resolution (∼0.8 Å) X-ray structures, while also highlighting the need for complementary neutron studies that can provide details of H atoms not provided by X-ray crystallography.

Coherent x-ray zoom condenser lens for diffractive and scanning microscopy.

PubMed

Kimura, Takashi; Matsuyama, Satoshi; Yamauchi, Kazuto; Nishino, Yoshinori

2013-04-22

We propose a coherent x-ray zoom condenser lens composed of two-stage deformable Kirkpatrick-Baez mirrors. The lens delivers coherent x-rays with a controllable beam size, from one micrometer to a few tens of nanometers, at a fixed focal position. The lens is suitable for diffractive and scanning microscopy. We also propose non-scanning coherent diffraction microscopy for extended objects by using an apodized focused beam produced by the lens with a spatial filter. The proposed apodized-illumination method will be useful in highly efficient imaging with ultimate storage ring sources, and will also open the way to single-shot coherent diffraction microscopy of extended objects with x-ray free-electron lasers.

Scanning force microscope for in situ nanofocused X-ray diffraction studies

PubMed Central

Ren, Zhe; Mastropietro, Francesca; Davydok, Anton; Langlais, Simon; Richard, Marie-Ingrid; Furter, Jean-Jacques; Thomas, Olivier; Dupraz, Maxime; Verdier, Marc; Beutier, Guillaume; Boesecke, Peter; Cornelius, Thomas W.

2014-01-01

A compact scanning force microscope has been developed for in situ combination with nanofocused X-ray diffraction techniques at third-generation synchrotron beamlines. Its capabilities are demonstrated on Au nano-islands grown on a sapphire substrate. The new in situ device allows for in situ imaging the sample topography and the crystallinity by recording simultaneously an atomic force microscope (AFM) image and a scanning X-ray diffraction map of the same area. Moreover, a selected Au island can be mechanically deformed using the AFM tip while monitoring the deformation of the atomic lattice by nanofocused X-ray diffraction. This in situ approach gives access to the mechanical behavior of nanomaterials. PMID:25178002

X-ray topography using the forward transmitted beam under multiple-beam diffraction conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsusaka, Y., E-mail: tsusaka@sci.u-hyogo.ac.jp; Takano, H.; Takeda, S.

2016-02-15

X-ray topographs are taken for a sapphire wafer with the [0001] surface normal, as an example, by forward transmitted synchrotron x-ray beams combined with two-dimensional electronic arrays in the x-ray detector having a spatial resolution of 1 μm. They exhibit no shape deformation and no position shift of the dislocation lines on the topographs. Since the topography is performed under multiple-beam diffraction conditions, the topographic images of a single diffraction (two-wave approximation condition) or plural diffractions (six-wave approximation condition) can be recorded without large specimen position changes. As usual Lang topographs, it is possible to determine the Burgers vector ofmore » each dislocation line. Because of high parallelism of the incoming x-rays and linear sensitivity of the electronic arrays to the incident x-rays, the present technique can be used to visualize individual dislocations in single crystals of the dislocation density as high as 1 × 10{sup 5} cm{sup −2}.« less

Constructing a Catalytic Cycle for C-F to C-X (X = O, S, N) Bond Transformation Based on Gold-Mediated Ligand Nucleophilic Attack.

PubMed

Hu, Ji-Yun; Zhang, Jing; Wang, Gao-Xiang; Sun, Hao-Ling; Zhang, Jun-Long

2016-03-07

A tricoordinated gold(I) chloride complex, tBuXantphosAuCl, supported by a sterically bulky 9,9-dimethyl-4,5-bis(di-tert-butylphosphino)xanthene ligand (tBuXantphos) was synthesized. This complex features a remarkably longer Au-Cl bond length [2.632(1) Å] than bicoordinated linear gold complexes (2.27-2.30 Å) and tricoordinated XantphosAuCl [2.462(1) Å]. Single-crystal X-ray diffraction analysis of a cocrystal of tBuXantphosAuCl and pentafluoronitrobenzene (PFNB) and UV-vis spectroscopic titration experiments revealed the existence of an anion-π interaction between the Cl anion ligand and PFNB. Stoichiometric reaction between PFNB and tBuXantphosAuOtBu, after replacement of Cl by a more nucleophilic tBuO anion ligand, showed higher reactivity and para selectivity in the transformation of C-F to C-OtBu bond, distinctively different from that when only KOtBu was used (ortho selectivity) under the identical condition. Mechanistic studies including density functional theory calculations suggested a gold-mediated nucleophilic ligand attack of the C-F bond pathway via an SNAr process. On the basis of these results, using trimethylsilyl derivatives TMS-X (X = OMe, SEt, NEt2) as the nucleophilic ligand source and the fluorine acceptor, catalytic transformation of the C-F bond of aromatic substrates to the C-X (X = O, S, N) bond was achieved with tBuXantphosAuCl as the catalyst (up to 20 turnover numbers).

Multiple defocused coherent diffraction imaging: method for simultaneously reconstructing objects and probe using X-ray free-electron lasers.

PubMed

Hirose, Makoto; Shimomura, Kei; Suzuki, Akihiro; Burdet, Nicolas; Takahashi, Yukio

2016-05-30

The sample size must be less than the diffraction-limited focal spot size of the incident beam in single-shot coherent X-ray diffraction imaging (CXDI) based on a diffract-before-destruction scheme using X-ray free electron lasers (XFELs). This is currently a major limitation preventing its wider applications. We here propose multiple defocused CXDI, in which isolated objects are sequentially illuminated with a divergent beam larger than the objects and the coherent diffraction pattern of each object is recorded. This method can simultaneously reconstruct both objects and a probe from the coherent X-ray diffraction patterns without any a priori knowledge. We performed a computer simulation of the prposed method and then successfully demonstrated it in a proof-of-principle experiment at SPring-8. The prposed method allows us to not only observe broad samples but also characterize focused XFEL beams.

Angular rheology study of colloidal nanocrystals using Coherent X-ray Diffraction

NASA Astrophysics Data System (ADS)

Liang, Mengning; Harder, Ross; Robinson, Ian

2007-03-01

A new method using coherent x-ray diffraction provides a way to investigate the rotational motion of a colloidal suspension of crystals in real time. Coherent x-ray diffraction uses the long coherence lengths of synchrotron sources to illuminate a nanoscale particle coherently over its spatial dimensions. The penetration of high energy x-rays into various media allows for in-situ measurements making it ideal for suspensions. This technique has been used to image the structure of nanocrystals for some time but also has the capability of providing information about the orientation and dynamics of crystals. The particles are imaged in a specific diffraction condition allowing us to determine their orientation and observe how they rotate in real time with exceptional resolution. Such sensitivity allows for the study of rotational Brownian motion of nanocrystals in various suspensions and conditions. We present a study of the angular rheology of alumina and TiO2 colloidal nanocrystals in media using coherent x-ray diffraction.

Characterization of polycrystalline materials using synchrotron X-ray imaging and diffraction techniques

NASA Astrophysics Data System (ADS)

Ludwig, W.; King, A.; Herbig, M.; Reischig, P.; Marrow, J.; Babout, L.; Lauridsen, E. M.; Proudhon, H.; Buffière, J. Y.

2010-12-01

The combination of synchrotron radiation x-ray imaging and diffraction techniques offers new possibilities for in-situ observation of deformation and damage mechanisms in the bulk of polycrystalline materials. Minute changes in electron density (i.e., cracks, porosities) can be detected using propagation based phase contrast imaging, a 3-D imaging mode exploiting the coherence properties of third generation synchrotron beams. Furthermore, for some classes of polycrystalline materials, one may use a 3-D variant of x-ray diffraction imaging, termed x-ray diffraction contrast tomography. X-ray diffraction contrast tomography provides access to the 3-D shape, orientation, and elastic strain state of the individual grains from polycrystalline sample volumes containing up to thousand grains. Combining both imaging modalities, one obtains a comprehensive description of the materials microstructure at the micrometer length scale. Repeated observation during (interrupted) mechanical tests provide unprecedented insight into crystallographic and grain microstructure related aspects of polycrystalline deformation and degradation mechanisms.

Quantitative analysis of thoria phase in Th-U alloys using diffraction studies

NASA Astrophysics Data System (ADS)

Thakur, Shital; Krishna, P. S. R.; Shinde, A. B.; Kumar, Raj; Roy, S. B.

2017-05-01

In the present study the quantitative phase analysis of Th-U alloys in bulk form namely Th-52 wt% U and Th-3wt%U has been performed over the data obtained from both X ray diffraction and neutron diffraction technique using Rietveld method of FULLPROF software. Quantifying thoria (ThO2) phase present in bulk of the sample is limited due to surface oxidation and low penetration of x rays in high Z material. Neutron diffraction study probing bulk of the samples has been presented in comparison with x-ray diffraction study.

Selenium single-wavelength anomalous diffraction de novo phasing using an X-ray-free electron laser

DOE PAGES

Hunter, Mark S.; Yoon, Chun Hong; DeMirci, Hasan; ...

2016-11-04

Structural information about biological macromolecules near the atomic scale provides important insight into the functions of these molecules. To date, X-ray crystallography has been the predominant method used for macromolecular structure determination. However, challenges exist when solving structures with X-rays, including the phase problem and radiation damage. X-ray-free electron lasers (X-ray FELs) have enabled collection of diffraction information before the onset of radiation damage, yet the majority of structures solved at X-ray FELs have been phased using external information via molecular replacement. De novo phasing at X-ray FELs has proven challenging due in part to per-pulse variations in intensity andmore » wavelength. Here we report the solution of a selenobiotinyl-streptavidin structure using phases obtained by the anomalous diffraction of selenium measured at a single wavelength (Se-SAD) at the Linac Coherent Light Source. Finally, our results demonstrate Se-SAD, routinely employed at synchrotrons for novel structure determination, is now possible at X-ray FELs.« less

Macromolecular structures probed by combining single-shot free-electron laser diffraction with synchrotron coherent X-ray imaging.

PubMed

Gallagher-Jones, Marcus; Bessho, Yoshitaka; Kim, Sunam; Park, Jaehyun; Kim, Sangsoo; Nam, Daewoong; Kim, Chan; Kim, Yoonhee; Noh, Do Young; Miyashita, Osamu; Tama, Florence; Joti, Yasumasa; Kameshima, Takashi; Hatsui, Takaki; Tono, Kensuke; Kohmura, Yoshiki; Yabashi, Makina; Hasnain, S Samar; Ishikawa, Tetsuya; Song, Changyong

2014-05-02

Nanostructures formed from biological macromolecular complexes utilizing the self-assembly properties of smaller building blocks such as DNA and RNA hold promise for many applications, including sensing and drug delivery. New tools are required for their structural characterization. Intense, femtosecond X-ray pulses from X-ray free-electron lasers enable single-shot imaging allowing for instantaneous views of nanostructures at ambient temperatures. When combined judiciously with synchrotron X-rays of a complimentary nature, suitable for observing steady-state features, it is possible to perform ab initio structural investigation. Here we demonstrate a successful combination of femtosecond X-ray single-shot diffraction with an X-ray free-electron laser and coherent diffraction imaging with synchrotron X-rays to provide an insight into the nanostructure formation of a biological macromolecular complex: RNA interference microsponges. This newly introduced multimodal analysis with coherent X-rays can be applied to unveil nano-scale structural motifs from functional nanomaterials or biological nanocomplexes, without requiring a priori knowledge.

Covalently Bonded Three-Dimensional Carbon Nanotube Solids via Boron Induced Nanojunctions

DTIC Science & Technology

2012-04-13

Novel Carbon Morphologies: From Covalent Y-Junctions to Sea - Urchin -Like Structures. Adv. Func. Mater. 19, 1193–1199 (2009). 15. Sumpter, B. G. et al...amorphous carbon as depicted from SEM (Fig. 1c). The X-ray powder diffraction pattern shows that as-produced CBXMWNT sponges are indeed crystalline and...material as-produced; (b) shows photograph of the flexibility and mechanical stablility upon bending the sample (a) by hand; (c) SEM image after ion

Surface Modification and Nanojunction Fabrication with Molecular Metal Wires

DTIC Science & Technology

2012-12-21

single - crystal X-ray diffraction studies of 2 and 3. Both the single - crystal structural data of 2 and 3 and the spectroscopic/voltammetric data...structure, magnetic properties, and single -molecule conductance of two new trinuclear metal string complexes, [Ni3(dzp)4(NCS)2] (2) and [ Co3 (dzp)4(NCS...modifying the crystallization conditions. The [s- Co3 (dpa)4(Cl)2] contains a symmetrical tricobalt framework with identical Co–Co bond lengths (2.34 Å

Exploration of New Principles in Spintronics Based on Topological Insulators (Option 1)

DTIC Science & Technology

2012-05-14

on the surface and found that our crystals are exceedingly homogeneous (Supplementary Information). The persistently narrow X - ray diffraction peaks...modified Bridgman method (see Supplementary Information for details). X - ray diffraction measurements indicated the monotonic shrinkage of a and c axis...and annealing at that temperature for 4 days. X - ray diffraction analyses confirmed that all the samples have the same crystal structure (R 3m

Carbon nanohorns under cold compression to 40 GPa: Raman scattering and X-ray diffraction experiments

NASA Astrophysics Data System (ADS)

Li, Bo; Nan, Yanli; Zhao, Xiang; Song, Xiaolong; Li, Haining; Wu, Jie; Su, Lei

2017-11-01

We report a high-pressure behavior of carbon nanohorns (CNHs) to 40 GPa at ambient temperature by in situ Raman spectroscopy and synchrotron radiation x-ray diffraction (XRD) in a diamond anvil cell. In Raman measurement, multiple structural transitions are observed. In particular, an additional band at ˜1540 cm-1 indicative of sp3 bonding is shown above 35 GPa, but it reverses upon releasing pressure, implying the formation of a metastable carbon phase having both sp2 and sp3 bonds. Raman frequencies of all bands (G, 2D, D + G, and 2D') are dependent upon pressure with respective pressure coefficients, among which the value for the G band is as small as ˜2.65 cm-1 GPa-1 above 10 GPa, showing a superior high-pressure structural stability. Analysis based on mode Grüneisen parameter demonstrates the similarity of high-pressure behavior between CNHs and single-walled carbon nanotubes. Furthermore, the bulk modulus and Grüneisen parameter for the G band of CNHs are calculated to be ˜33.3 GPa and 0.1, respectively. In addition, XRD data demonstrate that the structure of post-graphite phase derives from surface nanohorns. Based on topological defects within conical graphene lattice, a reasonable transformation route from nanohorns to the post-graphite phase is proposed.

Solid dispersions of Myricetin with enhanced solubility: Formulation, characterization and crystal structure of stability-impeding Myricetin monohydrate crystals

NASA Astrophysics Data System (ADS)

Mureşan-Pop, M.; Pop, M. M.; Borodi, G.; Todea, M.; Nagy-Simon, T.; Simon, S.

2017-08-01

Three solid dispersion forms of Myricetin combined with the Polyvinylpyrrolidone were successfully prepared by spray drying method, and characterized by X-ray powder diffraction, thermal analysis, infrared spectroscopy and optical microscopy. Zeta potential measurements provided indications on solid dispersions stability in aqueous suspension related to their storage at elevated temperature and relative humidity, which depends on the Myricetin load. By increase of Myricetin load, the stability of the solid dispersion is impeded due to growth of Myricetin monohydrate crystals. The amorphous dispersions with 10% and 50% Myricetin load are stable and, compared to pure Myricetin, their aqueous solubility is enhanced by a factor of 47 and 13, respectively. The dispersion with 80% Myricetin load is unstable on storage, and this behavior acts in conjunction with the development of Myricetin monohydrate crystals. Single-crystal X-ray diffraction results obtained for Myricetin monohydrate reveal a structure of an infinite 2D network of hydrogen-bonded molecules involving all six hydroxyl groups of Myricetin. The water molecules are positioned in between the infinite chains, and contribute via H-bonds to robust crystal packing. The calculated needle-like morphology of monohydrate form is in agreement with the optical microscopy results. The study shows that the solid amorphous dispersions with up to 50% Myricetin load are a viable option for achieving substantial solubility improvement of Myricetin, and supports their potential use in pharmaceutical applications.

Preparation and Structural Properties of InIII–H Complexes

PubMed Central

Sickerman, Nathaniel S.; Henry, Renée M.; Ziller, Joseph W.

2013-01-01

The use of the tripodal ligands tris[(N'-tert-butylureaylato)-N-ethyl]aminato ([H3buea]3−) and the sulfonamide-based N,N',N"-[2,2',2"-nitrilotris(ethane-2,1-diyl)]tris(2,4,6-trimethylbenzene-sulfonamidato) ([MST]3−) has led to the synthesis of two structurally distinct In(III)–OH complexes. The first example of a five-coordinate indium(III) complex with a terminal hydroxide ligand, K[InIIIH3buea(OH)], was prepared by addition of In(OAc)3 and water to a deprotonated solution of H6buea. X-ray diffraction analysis, as well as FTIR and 1H NMR spectroscopic methods, provided evidence for the formation of a monomeric In(III)–OH complex. The complex contains an intramolecular hydrogen bonding (H-bonding) network involving the In(III)–OH unit and [H3buea]3− ligand, which aided in isolation of the complex. Isotope labeling studies verified the source of the hydroxo ligand as water. Treatment of the [InIIIMST] complex with a mixture of 15-crown-5 ether and NaOH led to isolation of the complex [15-crown-5⊃NaI-(μ-OH)-InIIIMST], whose solid-state structure was confirmed using X-ray diffraction methods. Nuclear magnetic resonance studies on this complex suggest it retains its heterobimetallic structure in solution. PMID:25309019

Powder X-ray diffraction, infrared and 13C NMR spectroscopic studies of the homologous series of some solid-state zinc(II) and sodium(I) n-alkanoates

NASA Astrophysics Data System (ADS)

Nelson, Peter N.; Taylor, Richard A.

2015-03-01

A comparative study of the room temperature molecular packing and lattice structures for the homologous series of zinc(II) and sodium(I) n-alkanoates adduced from Fourier transform infrared and solid-state 13C NMR spectroscopic data in conjunction with X-ray powder diffraction measurements is carried out. For zinc carboxylates, metal-carboxyl bonding is via asymmetric bridging bidentate coordination whilst for the sodium adducts, coordination is via asymmetric chelating bidentate bonding. All compounds are packed in a monoclinic crystal system. Furthermore, the fully extended all-trans hydrocarbon chains are arranged as lamellar bilayers. For zinc compounds, there is bilayer overlap, for long chain adducts (nc > 8) but not for sodium compounds where methyl groups from opposing layers in the lamellar are only closely packed. Additionally, the hydrocarbon chains are extended along the a-axis of the unit cell for zinc compounds whilst for sodium carboxylates they are extended along the c-axis. These packing differences are responsible for different levels of Van der Waals effects in the lattices of these two series of compounds, hence, observed odd-even alternation is different. The significant difference in lattice packing observed for these two series of compounds is proposed to be due to the difference in metal-carboxyl coordination mode, arising from the different electronic structure of the central metal ions.

Structure elucidation of 3-[1-(6-methoxy-2-naphtyl)ethyl]-6-(2,4-dichlorophenyl)-7H-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazine, C 23H 18Cl 2N 4OS from synchrotron X-ray powder diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gündoğdu, Gülsüm; Aytaç, Sevim Peri; Müller, Melanie

The 3-[1-(6-methoxy-2-naphtyl)ethyl]-6-(2,4-dichlorophenyl)-7H-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazine, C 23H 18Cl 2N 4OS compound was synthesized, as a member of the family of novel potential anticancer agents. The structure of the title compound was characterized by IR, 1H-NMR, mass spectroscopy, and elemental analysis, previously. In this study, the crystal structure of this compound has been determined from synchrotron X-ray powder diffraction data. The crystal structure was solved by simulated annealing and the final structure was achieved by Rietveld refinement method using soft restrains on all interatomic bond lengths and angles. This compound crystallizes in space groupP21,Z= 2, with the unit-cell parametersa= 15.55645(11) Å,b= 8.61693(6) Å,c= 8.56702(6)more » Å,β= 104.3270(4)°, andV= 1112.68(1) Å 3. In the crystal structure, strong C-H∙∙∙πand weak intermolecular hydrogen-bonding interactions link the molecules into a three-dimensional network. The molecules are in a head-to-head arrangement in the unit cell.« less

Niclosamide methanol solvate and niclosamide hydrate: structure, solvent inclusion mode and implications for properties.

PubMed

Harriss, Bethany I; Wilson, Claire; Radosavljevic Evans, Ivana

2014-08-01

Structural studies have been carried out of two solid forms of niclosamide [5-chloro-N-(2-chloro-4-nitrophenyl)-2-hydroxybenzamide, NCL], a widely used anthelmintic drug, namely niclosamide methanol monosolvate, C13H8Cl2N2O4·CH3OH or NCL·MeOH, and niclosamide monohydrate, denoted HA. The structure of the methanol solvate obtained from single-crystal X-ray diffraction is reported for the first time, elucidating the key host-guest hydrogen-bonding interactions which lead to solvate formation. The essentially planar NCL host molecules interact via π-stacking and pack in a herringbone-type arrangement, giving rise to channels along the crystallographic a axis in which the methanol guest molecules are located. The methanol and NCL molecules interact via short O-H...O hydrogen bonds. Laboratory powder X-ray diffraction (PXRD) measurements reveal that the initially phase-pure NCL·MeOH solvate readily transforms into NCL monohydrate within hours under ambient conditions. PXRD further suggests that the NCL monohydrate, HA, is isostructural with the NCL·MeOH solvate. This is consistent with the facile transformation of the methanol solvate into the hydrate when stored in air. The crystal packing and the topology of guest-molecule inclusion are compared with those of other NCL solvates for which the crystal structures are known, giving a consistent picture which correlates well with known experimentally observed desolvation properties.

Synthesis and characterization of Mg-Al-layered double hydroxides intercalated with cubane-1,4-dicarboxylate anions.

PubMed

Rezvani, Zolfaghar; Arjomandi Rad, Farzad; Khodam, Fatemeh

2015-01-21

In the present work, Mg2Al-layered double hydroxide (LDH) intercalated with cubane-1,4-dicarboxylate anions was prepared from the reaction of solutions of Mg(ii) and Al(iii) nitrate salts with an alkaline solution of cubane-1,4-dicarboxylic acid by using the coprecipitation method. The successful preparation of a nanohybrid of cubane-1,4-dicarboxylate(cubane-dc) anions with LDH was confirmed by powder X-ray diffraction, FTIR spectroscopy and thermal gravimetric analysis (TGA). The increase in the basal spacing of LDHs from 8.67 Å to 13.40 Å shows that cubane-dc anions were successfully incorporated into the interlayer space. Thermogravimetric analyses confirm that the thermal stability of the intercalated cubane-dc anions is greater than that of the pure form before intercalation because of host-guest interactions involving hydrogen bonds. The interlayer structure, hydrogen bonding, and subsequent distension of LDH compounds containing cubane-dc anions were shown by molecular simulation. The RDF (radial distribution function), mean square displacement (MSD), and self-diffusion coefficient were calculated using the trajectory files on the basis of molecular dynamics (MD) simulations, and the results indicated that the cubane-dc anions were more stable when intercalated into the LDH layers. A good agreement was obtained between calculated and measured X-ray diffraction patterns and between experimental and calculated basal spacings.

Molecular beam epitaxial growth and characterization of InSb{sub 1-x}N{sub x} on GaAs for long wavelength infrared applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patra, Nimai C.; Bharatan, Sudhakar; Li, Jia

2012-04-15

Recent research progress and findings in InSbN have attracted great attention due to its use in long wavelength infrared applications. A large bandgap reduction in InSb resulting from high N incorporation with minimal crystal defects is challenging due to relatively small atomic size of N. Hence optimization of growth conditions plays an important role in the growth of high-quality InSbN epilayers for device purposes. In this paper, we report on the correlation of structural, vibrational, electrical, and optical properties of molecular beam epitaxially grown InSbN epilayers grown on GaAs substrates, as a function of varying growth temperatures. Two dimensional growthsmore » of InSb and InSbN were confirmed from dynamic reflection high energy electron diffraction patterns and growth parameters were optimized. High crystalline quality of the epilayers is attested to by a low full width at half maximum of 200 arcsec from high resolution x-ray diffraction (HRXRD) scans and by the high intensity and well-resolved InSb longitudinal optical (LO) and 2{sup nd} order InSb LO mode observed from micro-Raman spectroscopy. The N incorporation in these InSbN epilayers is estimated to be 1.4% based on HRXRD simulation. X-ray photoelectron spectroscopy (XPS) studies reveal that most of the N present in the layers are in the form of In-N bonding. Variation of the lattice disorder with growth temperature is correlated with the types of N bonding present, the carrier concentration and mobility, observed in the corresponding XPS spectra and Hall measurements, respectively. XPS analysis, HRXRD scans, and Raman spectral analysis indicate that lower growth temperature favors In-N bonding which dictates N incorporation in the substitutional sites and lattice disorder, whereas, high growth temperature promotes the formation of In-N-Sb bonding. The best room temperature and 77 K electrical transport parameters and maximum redshift in the absorption edge have been achieved in the InSbN epilayer grown in the 290 deg. C {approx} 330 deg. C temperature range.« less

Efficient modeling of Bragg coherent x-ray nanobeam diffraction

DOE PAGES

Hruszkewycz, S. O.; Holt, M. V.; Allain, M.; ...

2015-07-02

X-ray Bragg diffraction experiments that utilize tightly focused coherent beams produce complicated Bragg diffraction patterns that depend on scattering geometry, characteristics of the sample, and properties of the x-ray focusing optic. In this paper, we use a Fourier-transform-based method of modeling the 2D intensity distribution of a Bragg peak and apply it to the case of thin films illuminated with a Fresnel zone plate in three different Bragg scattering geometries. Finally, the calculations agree well with experimental coherent diffraction patterns, demonstrating that nanodiffraction patterns can be modeled at nonsymmetric Bragg conditions with this approach—a capability critical for advancing nanofocused x-raymore » diffraction microscopy.« less

HiSPoD: a program for high-speed polychromatic X-ray diffraction experiments and data analysis on polycrystalline samples

DOE PAGES

Sun, Tao; Fezzaa, Kamel

2016-06-17

Here, a high-speed X-ray diffraction technique was recently developed at the 32-ID-B beamline of the Advanced Photon Source for studying highly dynamic, yet non-repeatable and irreversible, materials processes. In experiments, the microstructure evolution in a single material event is probed by recording a series of diffraction patterns with extremely short exposure time and high frame rate. Owing to the limited flux in a short pulse and the polychromatic nature of the incident X-rays, analysis of the diffraction data is challenging. Here, HiSPoD, a stand-alone Matlab-based software for analyzing the polychromatic X-ray diffraction data from polycrystalline samples, is described. With HiSPoD,more » researchers are able to perform diffraction peak indexing, extraction of one-dimensional intensity profiles by integrating a two-dimensional diffraction pattern, and, more importantly, quantitative numerical simulations to obtain precise sample structure information.« less

Structure, glass transition temperature and spectroscopic properties of 10Li2O-xP2O5-(89-x)TeO2-1CuO (5≤x≤25 mol%) glass system.

PubMed

Upender, G; Babu, J Chinna; Mouli, V Chandra

2012-04-01

X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), energy dispersive X-ray spectrometry (EDS), differential scanning calorimetry (DSC), infrared (IR), Raman, electron paramagnetic resonance (EPR) and optical absorption studies on 10Li2O-xP2O5-(89-x)TeO2-1CuO glasses (where x=5, 10, 15, 20 and 25 mol%) have been carried out. The amorphous nature of the glasses was confirmed using XRD and FESEM measurements. The glass transition temperature (Tg) of glass samples have been estimated from DSC traces and found that the Tg increases with increasing P2O5 content. Both the IR and Raman studies have been showed that the present glass system consists of [TeO3], [TeO4], [PO3] and [PO4] units. The spin-Hamiltonian parameters such as g∥, g⊥, and A∥ have been determined from EPR spectra and it was found that the Cu2+ ion is present in tetragonal distorted octahedral site with [Formula: see text] as the ground state. Bonding parameters and bonding symmetry of Cu2+ ions have been calculated by correlating EPR and optical data and were found to be composition dependent. Copyright © 2012 Elsevier B.V. All rights reserved.

Monocrystalline silicon and the meta-shell approach to building x-ray astronomical optics

NASA Astrophysics Data System (ADS)

Zhang, William W.; Allgood, Kim D.; Biskach, Michael P.; Chan, Kai-Wing; Hlinka, Michal; Kearney, John D.; Mazzarella, James R.; McClelland, Ryan S.; Numata, Ai; Olsen, Lawrence G.; Riveros, Raul E.; Saha, Timo T.; Solly, Peter M.

2017-08-01

Angular resolution and photon-collecting area are the two most important factors that determine the power of an X-ray astronomical telescope. The grazing incidence nature of X-ray optics means that even a modest photon-collecting area requires an extraordinarily large mirror area. This requirement for a large mirror area is compounded by the fact that X-ray telescopes must be launched into, and operated in, outer space, which means that the mirror must be both lightweight and thin. Meanwhile the production and integration cost of a large mirror area determines the economical feasibility of a telescope. In this paper we report on a technology development program whose objective is to meet this three-fold requirement of making astronomical X-ray optics: (1) angular resolution, (2) photon-collecting area, and (3) production cost. This technology is based on precision polishing of monocrystalline silicon for making a large number of mirror segments and on the metashell approach to integrate these mirror segments into a mirror assembly. The meta-shell approach takes advantage of the axial or rotational symmetry of an X-ray telescope to align and bond a large number of small, lightweight mirrors into a large mirror assembly. The most important features of this technology include: (1) potential to achieve the highest possible angular resolution dictated by optical design and diffraction; and (2) capable of implementing every conceivable optical design, such as Wolter-I, WolterSchwarzschild, as well as other variations to one or another aspect of a telescope. The simplicity and modular nature of the process makes it highly amenable to mass production, thereby making it possible to produce very large X-ray telescopes in a reasonable amount of time and at a reasonable cost. As of June 2017, the basic validity of this approach has been demonstrated by finite element analysis of its structural, thermal, and gravity release characteristics, and by the fabrication, alignment, bonding, and X-ray testing of mirror modules. Continued work in the coming years will raise the technical readiness of this technology for use by SMEX, MIDEX, Probe, as well as major flagship missions.

Monocrystalline Silicon and the Meta-Shell Approach to Building X-Ray Astronomical Optics

NASA Technical Reports Server (NTRS)

Zhang, William W.; Allgood, Kim D.; Biskach, Michael P.; Chan, Kai-Wing; Hlinka, Michal; Kearney, John D.; Mazzarella, James R.; McClelland, Ryan S.; Numata, Ai; Olsen, Lawrence G.;

X-ray diffraction and X-ray standing-wave study of the lead stearate film structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blagov, A. E.; Dyakova, Yu. A.; Kovalchuk, M. V.

2016-05-15

A new approach to the study of the structural quality of crystals is proposed. It is based on the use of X-ray standing-wave method without measuring secondary processes and considers the multiwave interaction of diffraction reflections corresponding to different harmonics of the same crystallographic reflection. A theory of multiwave X-ray diffraction is developed to calculate the rocking curves in the X-ray diffraction scheme under consideration for a long-period quasi-one-dimensional crystal. This phase-sensitive method is used to study the structure of a multilayer lead stearate film on a silicon substrate. Some specific structural features are revealed for the surface layer ofmore » the thin film, which are most likely due to the tilt of the upper layer molecules with respect to the external normal to the film surface.« less

Molybdenum cell for x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures

NASA Astrophysics Data System (ADS)

Matsuda, Kazuhiro; Tamura, Kozaburo; Katoh, Masahiro; Inui, Masanori

2004-03-01

We have developed a sample cell for x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures. All parts of the cell are made of molybdenum which is resistant to the chemical corrosion of alkali metals. Single crystalline molybdenum disks electrolytically thinned down to 40 μm were used as the walls of the cell through which x rays pass. The crystal orientation of the disks was controlled in order to reduce the background from the cell. All parts of the cell were assembled and brazed together using a high-temperature Ru-Mo alloy. Energy dispersive x-ray diffraction measurements have been successfully carried out for fluid rubidium up to 1973 K and 16.2 MPa. The obtained S(Q) demonstrates the applicability of the molybdenum cell to x-ray diffraction measurements of fluid alkali metals at high temperatures and high pressures.

High-resolution ab initio three-dimensional x-ray diffraction microscopy

DOE PAGES

Chapman, Henry N.; Barty, Anton; Marchesini, Stefano; ...

2006-01-01

Coherent x-ray diffraction microscopy is a method of imaging nonperiodic isolated objects at resolutions limited, in principle, by only the wavelength and largest scattering angles recorded. We demonstrate x-ray diffraction imaging with high resolution in all three dimensions, as determined by a quantitative analysis of the reconstructed volume images. These images are retrieved from the three-dimensional diffraction data using no a priori knowledge about the shape or composition of the object, which has never before been demonstrated on a nonperiodic object. We also construct two-dimensional images of thick objects with greatly increased depth of focus (without loss of transverse spatialmore » resolution). These methods can be used to image biological and materials science samples at high resolution with x-ray undulator radiation and establishes the techniques to be used in atomic-resolution ultrafast imaging at x-ray free-electron laser sources.« less

Enhancing resolution in coherent x-ray diffraction imaging.

PubMed

Noh, Do Young; Kim, Chan; Kim, Yoonhee; Song, Changyong

2016-12-14

Achieving a resolution near 1 nm is a critical issue in coherent x-ray diffraction imaging (CDI) for applications in materials and biology. Albeit with various advantages of CDI based on synchrotrons and newly developed x-ray free electron lasers, its applications would be limited without improving resolution well below 10 nm. Here, we review the issues and efforts in improving CDI resolution including various methods for resolution determination. Enhancing diffraction signal at large diffraction angles, with the aid of interference between neighboring strong scatterers or templates, is reviewed and discussed in terms of increasing signal-to-noise ratio. In addition, we discuss errors in image reconstruction algorithms-caused by the discreteness of the Fourier transformations involved-which degrade the spatial resolution, and suggest ways to correct them. We expect this review to be useful for applications of CDI in imaging weakly scattering soft matters using coherent x-ray sources including x-ray free electron lasers.

A portable X-ray diffraction apparatus for in situ analyses of masters' paintings

NASA Astrophysics Data System (ADS)

Eveno, Myriam; Duran, Adrian; Castaing, Jacques

2010-09-01

It is rare that the analyses of materials in paintings can be carried out by taking micro-samples. Valuable works of art are best studied in situ by non-invasive techniques. For that purpose, a portable X-ray diffraction and fluorescence apparatus has been designed and constructed at the C2RMF. This apparatus has been used for paintings of Rembrandt, Leonardo da Vinci, Van Gogh, Mantegna, etc. Results are given to illustrate the performance of X-ray diffraction, especially when X-ray fluorescence does not bring sufficient information to conclude.

X-ray fractography on fatigue fractured surface of austenitic stainless steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yajima, Zenjiro; Tokuyama, Hideki; Kibayashi, Yasuo

1995-12-31

X-ray diffraction observation of the material internal structure beneath fracture surfaces provide fracture analysis with useful information to investigate the conditions and mechanisms of fracture. X-ray fractography is a generic name given to this technique. In the present study, X-ray fractography was applied to fatigue fracture surfaces of austenitic stainless steel (AISI 304) which consisted of solution treatment. The fatigue tests were carried out on compact tension (CT) specimens. The plastic strain on the fracture surface was estimated from measuring the line broadening of X-ray diffraction profiles. The line broadening of X-ray diffraction profiles was measured on and beneath fatiguemore » fracture surfaces. The depth of the plastic zone left on fracture surfaces was evaluated from the line broadening. The results are discussed on the basis of fracture mechanics.« less

Toward in situ x-ray diffraction imaging at the nanometer scale

NASA Astrophysics Data System (ADS)

Zatsepin, Nadia A.; Dilanian, Ruben A.; Nikulin, Andrei Y.; Gable, Brian M.; Muddle, Barry C.; Sakata, Osami

2008-08-01

We present the results of preliminary investigations determining the sensitivity and applicability of a novel x-ray diffraction based nanoscale imaging technique, including simulations and experiments. The ultimate aim of this nascent technique is non-destructive, bulk-material characterization on the nanometer scale, involving three dimensional image reconstructions of embedded nanoparticles and in situ sample characterization. The approach is insensitive to x-ray coherence, making it applicable to synchrotron and laboratory hard x-ray sources, opening the possibility of unprecedented nanometer resolution with the latter. The technique is being developed with a focus on analyzing a technologically important light metal alloy, Al-xCu (where x is 2.0-5.0 %wt). The mono- and polycrystalline samples contain crystallographically oriented, weakly diffracting Al2Cu nanoprecipitates in a sparse, spatially random dispersion within the Al matrix. By employing a triple-axis diffractometer in the non-dispersive setup we collected two-dimensional reciprocal space maps of synchrotron x-rays diffracted from the Al2Cu nanoparticles. The intensity profiles of the diffraction peaks confirmed the sensitivity of the technique to the presence and orientation of the nanoparticles. This is a fundamental step towards in situ observation of such extremely sparse, weakly diffracting nanoprecipitates embedded in light metal alloys at early stages of their growth.

Diffraction and Imaging Study of Imperfections of Protein Crystals with Coherent X-rays

NASA Technical Reports Server (NTRS)

Hu, Z. W.; Thomas, B. R.; Chernov, A. A.; Chu, Y. S.; Lai, B.

2004-01-01

High angular-resolution x-ray diffraction and phase contrast x-ray imaging were combined to study defects and perfection of protein crystals. Imperfections including line defects, inclusions and other microdefects were observed in the diffraction images of a uniformly grown lysozyme crystal. The observed line defects carry distinct dislocation features running approximately along the <110> growth front and have been found to originate mostly in a central growth area and occasionally in outer growth regions. Slow dehydration led to the broadening of a fairly symmetric 4 4 0 rocking curve by a factor of approximately 2.6, which was primarily attributed to the dehydration-induced microscopic effects that are clearly shown in diffraction images. X-ray imaging and diffraction characterization of the quality of apoferritin crystals will also be discussed in the presentation.

In Situ Neutron Diffraction of Rare-Earth Phosphate Proton Conductors Sr/Ca-doped LaPO4 at Elevated Temperatures

NASA Astrophysics Data System (ADS)

Al-Wahish, Amal; Al-Binni, Usama; Bridges, C. A.; Huq, A.; Bi, Z.; Paranthaman, M. P.; Tang, S.; Kaiser, H.; Mandrus, D.

Acceptor-doped lanthanum orthophosphates are potential candidate electrolytes for proton ceramic fuel cells. We combined neutron powder diffraction (NPD) at elevated temperatures up to 800° C , X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) to investigate the crystal structure, defect structure, thermal stability and surface topography. NPD shows an average bond length distortion in the hydrated samples. We employed Quasi-Elastic Neutron Scattering (QENS) and electrochemical impedance spectroscopy (EIS) to study the proton dynamics of the rare-earth phosphate proton conductors 4.2% Sr/Ca-doped LaPO4. We determined the bulk diffusion and the self-diffusion coefficients. Our results show that QENS and EIS are probing fundamentally different proton diffusion processes. Supported by the U.S. Department of Energy.

Silicon oxynitride films deposited by reactive high power impulse magnetron sputtering using nitrous oxide as a single-source precursor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hänninen, Tuomas, E-mail: tuoha@ifm.liu.se; Schmidt, Susann; Jensen, Jens

2015-09-15

Silicon oxynitride thin films were synthesized by reactive high power impulse magnetron sputtering of silicon in argon/nitrous oxide plasmas. Nitrous oxide was employed as a single-source precursor supplying oxygen and nitrogen for the film growth. The films were characterized by elastic recoil detection analysis, x-ray photoelectron spectroscopy, x-ray diffraction, x-ray reflectivity, scanning electron microscopy, and spectroscopic ellipsometry. Results show that the films are silicon rich, amorphous, and exhibit a random chemical bonding structure. The optical properties with the refractive index and the extinction coefficient correlate with the film elemental composition, showing decreasing values with increasing film oxygen and nitrogen content.more » The total percentage of oxygen and nitrogen in the films is controlled by adjusting the gas flow ratio in the deposition processes. Furthermore, it is shown that the film oxygen-to-nitrogen ratio can be tailored by the high power impulse magnetron sputtering-specific parameters pulse frequency and energy per pulse.« less

Control of the kerf size and microstructure in Inconel 738 superalloy by femtosecond laser beam cutting

NASA Astrophysics Data System (ADS)

Wei, J.; Ye, Y.; Sun, Z.; Liu, L.; Zou, G.

2016-05-01

Femtosecond laser beam cutting is becoming widely used to meet demands for increasing accuracy in micro-machining. In this paper, the effects of processing parameters in femtosecond laser beam cutting on the kerf size and microstructure in Inconel 738 have been investigated. The defocus, pulse width and scanning speed were selected to study the controllability of the cutting process. Adjusting and matching the processing parameters was a basic enhancement method to acquire well defined kerf size and the high-quality ablation of microstructures, which has contributed to the intensity clamping effect. The morphology and chemical compositions of these microstructures on the cut surface have been characterized by a scanning electron microscopy equipped with an energy dispersive X-ray spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Additionally, the material removal mechanism and oxidation mechanism on the Inconel 738 cut surface have also been discussed on the basis of the femtosecond laser induced normal vaporization or phase explosion, and trapping effect of the dangling bonds.

THE EFFECT OF SATELLITE LINES FROM THE X-RAY SOURCE ON X-RAY DIFFRACTION PEAKS

EPA Science Inventory

The article discusses the development of a method for relating reactivity to crystallite size and strain parameters obtained by the Warren-Averbach technique. EPA has been using crystallite size and strain data obtained from x-ray diffraction (XRD) peak profile analysis to predic...

History and Solution of the Phase Problem in theTheory of Structure Determination of Crystals from X-ray Diffraction Experiments

ScienceCinema

Wolf, Emil [University of Rochester, Rochester, New York, United States

2017-12-09

Since the pioneering work of Max von Laue on interference and diffraction of x-rays, carried out almost 100 years ago, numerous attempts have been made to determine structures of crystalline media from x-ray diffraction experiments. The usefulness of all of them has been limited by the inability of measuring phases of the diffracted beams. In this talk, the most important research carried out in this field will be reviewed and a recently obtained solution of the phase problem will be presented.

A Chemical Approach to Understanding Oxide Surface Structure and Reactivity

NASA Astrophysics Data System (ADS)

Enterkin, James Andrew

Transmission electron microscopy and diffraction are powerful tools for solving complex structural problems. They complement other analytical techniques, such as x-ray diffraction, elucidating problems which cannot be solved by other techniques. One area where they are of particularly great value is in the determination of surface structures. The research presented herein uses electron microscopy and diffraction as the primary experimental techniques in the development of a chemistry of surface structures. High-resolution electron microscopy revealed that the La4Cu 3MoO12 structure has turbostratic disorder and a lower symmetry space group (Pm) than was previously found. The refinement of the x-ray data was significantly improved by using a disordered model and the Pm space group. A bond valence analysis confirmed that the disordered structure is the superior model. Strontium titanate, SrTiO3, single crystal surfaces were examined principally via transmission electron diffraction. A homologous series with intergrowths was discovered on the (110) surface of strontium titanate, marking the first time that these important concepts of solid state chemistry have been found at the surface. Atmospheric adsorbates, such as H2O and CO2, were found to help to stabilize undercoordinated surface structures on the (100) surface. It was shown that chemical bonding, bond valence, atomic coordination, and stoichiometry greatly influence the development of surface structures. Additionally, such chemistry based analysis was demonstrated to be able to predict surface structure stability and reactivity. Application of a modified Wulff construction to the observed shape of strontium titanate nanocuboids revealed that the surface structure and particle stoichiometry are interlinked, with control over one allowing equally precise control over the other. Platinum nanoparticles on the strontium titanate nanocuboids were shown via high resolution electron microscopy to have cube-on-cube epitaxy, with the shape of the platinum nanoparticles governed by the Winterbottom construction. Precise modification of the support surface will therefore allow engineering of supported metal particles with precise control over which facets are exposed. These results suggest that control over the support surface chemistry can be used to engineer thermodynamically stable, face selective catalysts.

XRayView: a teaching aid for X-ray crystallography.

PubMed

Phillips, G N

1995-10-01

A software package, XRayView, has been developed that uses interactive computer graphics to introduce basic concepts of x-ray diffraction by crystals, including the reciprocal lattice, the Ewald sphere construction, Laue cones, the wavelength dependence of the reciprocal lattice, primitive and centered lattices and systematic extinctions, rotation photography. Laue photography, space group determination and Laue group symmetry, and the alignment of crystals by examination of reciprocal space. XRayView is designed with "user-friendliness" in mind, using pull-down menus to control the program. Many of the experiences of using real x-ray diffraction equipment to examine crystalline diffraction can be simulated. Exercises are available on-line to guide the users through many typical x-ray diffraction experiments.

Ammoniated alkali fullerides (ND(3))(x)NaA(2)C(60): ammonia specific effects and superconductivity.

PubMed

Margadonna, Serena; Aslanis, Efstathios; Prassides, Kosmas

2002-08-28

The crystal structure of the superconducting (ND(3))(x)()NaA(2)C(60) (0.7 < or = x < or = 1, A= K, Rb) fullerides (T(c)= 6-15 K) has been studied by synchrotron X-ray and neutron powder diffraction. It is face-centered cubic (fcc) to low temperatures with Na(+)-ND(3) pairs residing in the octahedral interstices. These are disordered over the corners of two "interpenetrating" cubes with the Na(+) ions and the N atoms displaced by approximately 2.0 A and approximately 0.5 A from the center of the site and statically disordered over the corners of the inner and outer cube, respectively. Close contacts between the D atoms of the ND(3) molecules and electron rich 6:6 C-C bonds of neighboring C(60) units provide the signature of weak N-D.pi hydrogen-bonding interactions, which control the intermolecular packing in the crystal and may determine the unusual superconducting properties.

Application of MEMS-based x-ray optics as tuneable nanosecond choppers

NASA Astrophysics Data System (ADS)

Chen, Pice; Walko, Donald A.; Jung, Il Woong; Li, Zhilong; Gao, Ya; Shenoy, Gopal K.; Lopez, Daniel; Wang, Jin

2017-08-01

Time-resolved synchrotron x-ray measurements often rely on using a mechanical chopper to isolate a set of x-ray pulses. We have started the development of micro electromechanical systems (MEMS)-based x-ray optics, as an alternate method to manipulate x-ray beams. In the application of x-ray pulse isolation, we recently achieved a pulse-picking time window of half a nanosecond, which is more than 100 times faster than mechanical choppers can achieve. The MEMS device consists of a comb-drive silicon micromirror, designed for efficiently diffracting an x-ray beam during oscillation. The MEMS devices were operated in Bragg geometry and their oscillation was synchronized to x-ray pulses, with a frequency matching subharmonics of the cycling frequency of x-ray pulses. The microscale structure of the silicon mirror in terms of the curvature and the quality of crystallinity ensures a narrow angular spread of the Bragg reflection. With the discussion of factors determining the diffractive time window, this report showed our approaches to narrow down the time window to half a nanosecond. The short diffractive time window will allow us to select single x-ray pulse out of a train of pulses from synchrotron radiation facilities.

Fabrication of high-resolution x-ray diffractive optics at King's College London

NASA Astrophysics Data System (ADS)

Charalambous, Pambos S.; Anastasi, Peter A. F.; Burge, Ronald E.; Popova, Katia

1995-09-01

The fabrication of high resolution x-ray diffractive optics, and Fresnel zone plates (ZPs) in particular, is a very demanding multifaceted technological task. The commissioning of more (and brighter) synchrotron radiation sources, has increased the number of x-ray imaging beam lines world wide. The availability of cheaper and more effective laboratory x-ray sources, has further increased the number of laboratories involved in x-ray imaging. The result is an ever increasing demand for x-ray optics with a very wide range of specifications, reflecting the particular type of x-ray imaging performed at different laboratories. We have been involved in all aspects of high resolution nanofabrication for a number of years, and we have explored many different methods of lithography, which, although unorthodox, open up possibilities, and increase our flexibility for the fabrication of different diffractive optical elements, as well as other types of nanostructures. The availability of brighter x-ray sources, means that the diffraction efficiency of the ZPs is becoming of secondary importance, a trend which will continue in the future. Resolution, however, is important and will always remain so. Resolution is directly related to the accuracy af pattern generation, as well as the ability to draw fine lines. This is the area towards which we have directed most of our efforts so far.

Inkjet printable-photoactive all inorganic perovskite films with long effective photocarrier lifetimes

NASA Astrophysics Data System (ADS)

Ilie, C. C.; Guzman, F.; Swanson, B. L.; Evans, I. R.; Costa, P. S.; Teeter, J. D.; Shekhirev, M.; Benker, N.; Sikich, S.; Enders, A.; Dowben, P. A.; Sinitskii, A.; Yost, A. J.

2018-05-01

Photoactive perovskite quantum dot films, deposited via an inkjet printer, have been characterized by x-ray diffraction and x-ray photoelectron spectroscopy. The crystal structure and bonding environment are consistent with CsPbBr3 perovskite quantum dots. The current–voltage (I–V) and capacitance–voltage (C–V) transport measurements indicate that the photo-carrier drift lifetime can exceed 1 ms for some printed perovskite films. This far exceeds the dark drift carrier lifetime, which is below 50 ns. The printed films show a photocarrier density 109 greater than the dark carrier density, making these printed films ideal candidates for application in photodetectors. The successful printing of photoactive-perovskite quantum dot films of CsPbBr3, indicates that the rapid prototyping of various perovskite inks and multilayers is realizable.

Two-photon x-ray diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stohr, J.

The interference pattern of a circular photon source has long been used to define the optical diffraction limit. Here we show the breakdown of conventional x-ray diffraction theory for the fundamental case of a “source”, consisting of a back-illuminated thin film in a circular aperture. When the conventional spontaneous x-ray scattering by atoms in the film is replaced at high incident intensity by stimulated resonant scattering, the film becomes the source of cloned photon twins and the diffraction pattern becomes self-focused beyond the diffraction limit. Furthermore, the case of cloned photon pairs is compared to and distinguished from entangled photonmore » pairs or biphotons.« less

Two-photon x-ray diffraction

DOE PAGES

Stohr, J.

2017-01-11

The interference pattern of a circular photon source has long been used to define the optical diffraction limit. Here we show the breakdown of conventional x-ray diffraction theory for the fundamental case of a “source”, consisting of a back-illuminated thin film in a circular aperture. When the conventional spontaneous x-ray scattering by atoms in the film is replaced at high incident intensity by stimulated resonant scattering, the film becomes the source of cloned photon twins and the diffraction pattern becomes self-focused beyond the diffraction limit. Furthermore, the case of cloned photon pairs is compared to and distinguished from entangled photonmore » pairs or biphotons.« less

Characterization of X80 and X100 Microalloyed Pipeline Steel Using Quantitative X-ray Diffraction

NASA Astrophysics Data System (ADS)

Wiskel, J. B.; Li, X.; Ivey, D. G.; Henein, H.

2018-06-01

Quantitative X-ray diffraction characterization of four (4) X80 and three (3) X100 microalloyed steels was undertaken. The effect of through-thickness position, processing parameters, and composition on the measured crystallite size, microstrain, and J index (relative magnitude of crystallographic texture) was determined. Microstructure analysis using optical microscopy, scanning electron microscopy, transmission electron microscopy, and electron-backscattered diffraction was also undertaken. The measured value of microstrain increased with increasing alloy content and decreasing cooling interrupt temperature. Microstructural features corresponding to crystallite size in the X80 steels were both above and below the detection limit for quantitative X-ray diffraction. The X100 steels consistently exhibited microstructure features below the crystallite size detection limit. The yield stress of each steel increased with increasing microstrain. The increase in microstrain from X80 to X100 is also associated with a change in microstructure from predominantly polygonal ferrite to bainitic ferrite.

Crystal structure of rivastigmine hydrogen tartrate Form I (Exelon®), C 14H 23N 2O 2(C 4H 5O 6)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaduk, James A.; Zhong, Kai; Gindhart, Amy M.

2016-03-08

The crystal structure of rivastigmine hydrogen tartrate has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Rivastigmine hydrogen tartrate crystallizes in space groupP2 1(#4) witha= 17.538 34(5),b= 8.326 89(2),c= 7.261 11(2) Å,β= 98.7999(2)°,V= 1047.929(4) Å 3, andZ= 2. The un-ionized end of the hydrogen tartrate anions forms a very strong hydrogen bond with the ionized end of another anion to form a chain. The ammonium group of the rivastigmine cation forms a strong discrete hydrogen bond with the carbonyl oxygen atom of the un-ionized end of the tartrate anion. These hydrogen bondsmore » form a corrugated network in thebc-plane. Both hydroxyl groups of the tartrate anion form intramolecular O–H···O hydrogen bonds. Several C–H···O hydrogen bonds appear to contribute to the crystal energy. The powder pattern is included in the Powder Diffraction File ™as entry 00-064-1501.« less

Diffractive-refractive optics: (+,-,-,+) X-ray crystal monochromator with harmonics separation.

PubMed

Hrdý, Jaromír; Mikulík, Petr; Oberta, Peter

2011-03-01

A new kind of two channel-cut crystals X-ray monochromator in dispersive (+,-,-,+) position which spatially separates harmonics is proposed. The diffracting surfaces are oriented so that the diffraction is inclined. Owing to refraction the diffracted beam is sagittally deviated. The deviation depends on wavelength and is much higher for the first harmonics than for higher harmonics. This leads to spatial harmonics separation. The idea is supported by ray-tracing simulation.

Superhard BC(3) in cubic diamond structure.

PubMed

Zhang, Miao; Liu, Hanyu; Li, Quan; Gao, Bo; Wang, Yanchao; Li, Hongdong; Chen, Changfeng; Ma, Yanming

2015-01-09

We solve the crystal structure of recently synthesized cubic BC(3) using an unbiased swarm structure search, which identifies a highly symmetric BC(3) phase in the cubic diamond structure (d-BC(3)) that contains a distinct B-B bonding network along the body diagonals of a large 64-atom unit cell. Simulated x-ray diffraction and Raman peaks of d-BC(3) are in excellent agreement with experimental data. Calculated stress-strain relations of d-BC(3) demonstrate its intrinsic superhard nature and reveal intriguing sequential bond-breaking modes that produce superior ductility and extended elasticity, which are unique among superhard solids. The present results establish the first boron carbide in the cubic diamond structure with remarkable properties, and these new findings also provide insights for exploring other covalent solids with complex bonding configurations.

Microscopic Description of the Ferroism in Lead-Free AlFeO3.

PubMed

Santos, Guilherme M; Catellani, Igor B; Santos, Ivair A; Guo, Ruyan; Bhalla, Amar S; Padilha, José Eduardo; Cótica, Luiz F

2018-04-23

The microscopic origin of the ferroic and multiferroic properties of AlFeO 3 have been carefully investigated. The maximum entropy method was applied to X-ray diffraction data and ab initio density functional theory calculations in order to obtain the electron density distributions and electric polarization. The study of chemical bonds shows that the bonds between Fe(3d) and O(2p) ions are anisotropic, leading to the configuration of shorter/longer and stronger/weaker bonds. This leads to electric polarization. Density of states calculations showed a magnetic polarization as a result of a weak ferromagnetic ordering. These results unambiguously show that AlFeO 3 is a multiferroic material and exhibits a magnetoelectric coupling at room temperature, as has already been shown by experiments.

Structural, vibrational and dielectric studies of (0.95)Pb(Zr{sub x}Ti{sub 1−x})O{sub 3}-(0.05)BiFeO{sub 3} nanoceramics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Subhash, E-mail: rk.dwivedi@jiit.ac.in; Singh, Vikash, E-mail: rk.dwivedi@jiit.ac.in; Dwivedi, R. K., E-mail: rk.dwivedi@jiit.ac.in

2014-04-24

(0.95)Pb(Zr{sub x}Ti{sub 1−x})O{sub 3}-(0.05)BiFeO{sub 3} nanoceramics with x=0.51, 0.53 and 0.55 were synthesized by sol-gel route. Rietveld refined X-ray powder diffraction pattern of the samples confirm the single phase formation of compounds with tetragonal structure (P4mm). FT-IR studies revealed that slight shift of phonon modes towards the lower wave number and increase in the bond length with increasing Zr{sup 4+} concentration. Room temperature dielectric properties of system revealed that relaxor characteristics of these samples. Ferroelectric hysteresis curve shows the decrease in polarization values with Zr concentration.

Syntheses, structural characterization, and DPPH radical scavenging activity of cocrystals of caffeine with 1- and 2-naphthoxyacetic acids

NASA Astrophysics Data System (ADS)

Suresh Kumar, G. S.; Seethalakshmi, P. G.; Sumathi, D.; Bhuvanesh, N.; Kumaresan, S.

2013-03-01

Caffeine:1-naphthoxyacetic acid [(caf)(1-naa)] and caffeine:2-naphthoxyacetic acid [(caf)(2-naa)] cocrystals have been synthesized and single crystals were grown by slow evaporation technique. The structures of the grown crystals were elucidated using single crystal X-ray diffraction analysis. Both the cocrystals belong to the monoclinic crystallographic system with space group P21/c, Z = 4, and α = γ = 90°, whereas β = 111.4244(18)° for [(caf)(1-naa)] and β = 109.281(6)° for [(caf)(2-naa)]. The crystal packing is predominantly stabilized by hydrogen bonding and π-π stacking interactions. The presence of unionized -COOH functional group in both the cocrystals was identified by FTIR spectral analysis. Thermal behavior and stability of both the cocrystals were studied by TGA/DTA analyses. Solvent-free formation of these cocrystals was confirmed by powder X-ray diffraction analyses. The theoretical energy of cocrystals showed that the formers have higher energy than cocrystals 1 and 2. DPPH radical scavenging activity of cocrystals 1 and 2 is slightly greater than the formers.

Liquid structure of dibutyl sulfoxide

DOE PAGES

Lo Celso, Fabrizio; Aoun, Bachir; Triolo, Alessandro; ...

2016-05-16

We present experimental (x-ray diffraction) data on the structure of liquid dibutyl sulfoxide at 320 K and rationalize them by means of Molecular Dynamics simulations. Not unexpectedly, DBSO bearing a strong dipolar moiety and two medium length, apolar, butyl chains, this compound turns out to be characterised by a distinct degree of polar-vs-apolar structural differentiation at the nm spatial scale that is fingerprinted in a low Q peak in its x-ray diffraction pattern. Similarly to, but to a larger extent than its shorter chain family members (such as DMSO), DBSO is also characterised by an enhanced dipole-dipole correlation that ismore » responsible for the moderate Kirkwood correlation factor as well as for the self-association detected in this compound. In conclusion, we show however that the supposedly relevant hydrogen bonding correlations between oxygen and butyl chain hydrogens are of limited extent and only in the case of α-hydrogens appreciable indication of the existence of such an interaction is found, but it turns out to be a mere consequence of the strong dipole-dipole correlation.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Josefsson, Gabriella; Gamstedt, E. Kristofer; Ahvenainen, Patrik

The mechanical performance of materials reinforced by cellulose nanofibrils is highly affected by the orientation of these fibrils. This paper investigates the nanofibril orientation distribution of films of partly oriented cellulose nanofibrils. Stripes of hydrogel films were subjected to different amount of strain and, after drying, examined with X-ray diffraction to obtain the orientation of the nanofibrils in the films, caused by the stretching. The cellulose nanofibrils had initially a random in-plane orientation in the hydrogel films and the strain was applied to the films before the nanofibrils bond tightly together, which occurs during drying. The stretching resulted in amore » reorientation of the nanofibrils in the films, with monotonically increasing orientation towards the load direction with increasing strain. Estimation of nanofibril reorientation by X-ray diffraction enables quantitative comparison of the stretch-induced orientation ability of different cellulose nanofibril systems. The reorientation of nanofibrils as a consequence of an applied strain is also predicted by a geometrical model of deformation of nanofibril hydrogels. Conversely, in high-strain cold-drawing of wet cellulose nanofibril materials, the enhanced orientation is promoted by slipping of the effectively stiff fibrils.« less

Screening and structural elucidation of the zwitterionic cocrystal o-picolinic acid with p-nitro aniline

NASA Astrophysics Data System (ADS)

Mekala, R.; Jagdish, P.; Mathammal, R.; Sangeetha, K.

2017-04-01

The cocrystal was screened by solvent drop grinding method and the crystals were grown by slow evaporation method at ambient conditions. The cocrystal formation of o-picolinic acid with p-nitro aniline was initially analysed by powder X-ray diffraction. Further the structural properties of the grown crystal were confirmed by the single X-ray diffraction which indicates that the cocrystal were connected by the strong N+sbnd H-⋯O hydrogen bond interaction. The cell parameters of the grown crystal were a = 14.2144(5) Å, b = 5.7558(2) Å, c = 16.0539(6) Å. The functional groups were identified using Fourier transform infrared and Raman spectral analysis. The excitation and emission state of the sample was analysed by the UV-Visible and Fluorescence studies. The red emission was observed from the Fluorescence studies. NMR studies revealed the chemical shift of the cocrystal. Thermal stability and its melting behaviour were studied by TGA and DSC analytical techniques. Electrical behaviour was studied using the dielectric studies. The intermolecular charge transfer within the molecule were analysed using HOMO- LUMO plots.

Synthesis and luminescence properties of cinnamide based nanohybrid materials containing Eu (II) ions

NASA Astrophysics Data System (ADS)

Kiran Kumar, A. B. V.; Jayasimhadri, M.; Cha, Hyeongrae; Chen, Kuangcai; Lim, Jae-Min; Lee, Yong-Ill

2011-07-01

In the present work, the cinnamide based organic-inorganic hybrid luminescent materials were prepared by using sol-gel technique, in which both the components are covalently linked via Si-C bonds. The organic precursor N-(3-(triethoxysilyl)propyl)cinnamide (Cn-Si) was synthesized by (3-aminopropyl) triethoxysilane being reacted with cinnamoyal chloride. Finally, novel hybrid materials were prepared successfully through hydrolysis and polycondensation processes between the alkoxide groups of precursors Cn-Si and tetraethylorthosilane (TEOS) in the presence of europium nitrate. We have characterized thoroughly the prepared samples using FT-IR, thermal analysis (TGA/DTA), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS) and photoluminescence (PL) spectroscopy. The results indicate that these materials exhibit the excellent thermal stability up to 350 °C. The X-ray diffraction patterns confirmed the amorphous nature of the developed materials. The rare-earth doped hybrid materials have exhibited an intense green emission at 530 nm with CIE chromaticity coordinates (0.4801, 0.4669). Whereas, the un-doped one gives some remarkable blue emission properties under UV excitation.

Structural and magnetic properties of Ni0.8M0.2Fe2O4 (M = Cu, Co) nano-crystalline ferrites

NASA Astrophysics Data System (ADS)

Vijaya Babu, K.; Satyanarayana, G.; Sailaja, B.; Santosh Kumar, G. V.; Jalaiah, K.; Ravi, M.

2018-06-01

Nano-crystalline nickel ferrites are interesting materials due to their large physical and magnetic properties. In the present work, two kinds of spinel ferrites Ni0.8M0.2Fe2O4 (M = Cu, Co) are synthesized by using sol-gel auto-combustion method and the results are compared with NiFe2O4. The structural properties of synthesized ferrites are determined by using X-ray powder diffraction; scanning electron microscope and Fourier transform infrared spectroscopy. The cation distribution obtained from X-ray diffraction show that cobalt/copper occupies only tetrahedral site in spinel lattice. The lattice constant increases with the substitution of cobalt/copper. The structural parameters like bond lengths, tetrahedral and octahedral edges have been varied with the substitution. The microstructural study is carried out by using SEM technique and the average grain size is increased with nickel ferrite. The initial permeability (μi) is improving with the substitution. The observed g-value from ESR is approximately equal to standard value.

A luminescent silver-saccharinato complex with S, S-diphenylsulfimide: Synthesis, spectroscopic, thermal, structural and DFT computational studies

NASA Astrophysics Data System (ADS)

Gumus, Sedat; Hamamci, Sevim; Yilmaz, V. T.; Kazak, Canan

2007-02-01

A new silver(I)-saccharinato (sac) complex with S, S-diphenylsulfimide, [Ag(sac)(Ph 2SNH)], has been prepared and characterized by elemental analysis, IR spectroscopy, thermal analysis and single crystal X-ray diffraction. X-ray diffraction analyses show that the title complex has a monomeric structure containing linearly coordinated silver(I) ion with an N-Ag-N angle of 173.80(10)°. The individual molecules are linked by strong N-H⋯O hydrogen bonds and aromatic stacking π⋯π interactions and packing of the molecules is further reinforced by C-H⋯π interactions. Ph 2SNH and [Ag(sac)(Ph 2SNH)] in solution at room temperature display intense blue luminescence with emission maxima at 380 and 408 nm, respectively. The photoluminescence properties have been investigated by DFT calculations, showing that the luminescence properties of the Ph 2SNH are due to intraligand transitions, while for the silver(I) complex, the luminescence was originated from several transitions including intraligand transitions and metal-to-ligand charge transfer (MLCT).

Room Temperature Elastic Moduli and Vickers Hardness of Hot-Pressed LLZO Cubic Garnet

DTIC Science & Technology

2012-01-01

polishing compounds, Leco, St. Joseph, MI). X - ray diffraction and scanning electron microscopy (SEM) The microstructure of the hot-pressed specimens...was examined on uncoated fracture surfaces by SEM with an accelerating voltage of 1 and 3 kV. Phase purity was evaluated from X - ray diffraction data...the micro- structure appeared to be homogenous for the two hot- pressed LLZO specimens included in this study (Fig. 1). X - ray diffraction confirmed that

Effect of Biaxial Strain on the Phase Transitions of Ca (Fe1 -xCox)2As2

NASA Astrophysics Data System (ADS)

Böhmer, A. E.; Sapkota, A.; Kreyssig, A.; Bud'ko, S. L.; Drachuck, G.; Saunders, S. M.; Goldman, A. I.; Canfield, P. C.

2017-03-01

We study the effect of applied strain as a physical control parameter for the phase transitions of Ca (Fe1 -xCox)2As2 using resistivity, magnetization, x-ray diffraction, and Fe 57 Mössbauer spectroscopy. Biaxial strain, namely, compression of the basal plane of the tetragonal unit cell, is created through firm bonding of samples to a rigid substrate via differential thermal expansion. This strain is shown to induce a magnetostructural phase transition in originally paramagnetic samples, and superconductivity in previously nonsuperconducting ones. The magnetostructural transition is gradual as a consequence of using strain instead of pressure or stress as a tuning parameter.

Method for improve x-ray diffraction determinations of residual stress in nickel-base alloys

DOEpatents

Berman, Robert M.; Cohen, Isadore

1990-01-01

A process for improving the technique of measuring residual stress by x-ray diffraction in pieces of nickel-base alloys which comprises covering part of a predetermined area of the surface of a nickel-base alloy with a dispersion, exposing the covered and uncovered portions of the surface of the alloy to x-rays by way of an x-ray diffractometry apparatus, making x-ray diffraction determinations of the exposed surface, and measuring the residual stress in the alloy based on these determinations. The dispersion is opaque to x-rays and serves a dual purpose since it masks off unsatisfactory signals such that only a small portion of the surface is measured, and it supplies an internal standard by providing diffractogram peaks comparable to the peaks of the nickel alloy so that the alloy peaks can be very accurately located regardless of any sources of error external to the sample.

Synthesis and Crystal Structure of a Chalcone Derivative

NASA Astrophysics Data System (ADS)

Singh, Vikram D.; Salian, Vinutha V.; Narayana, B.; Sarojini, B. K.; Kamni; Anthal, Sumati; Kant, Rajni

2017-12-01

(2E)-3-(anthrance-9-yl)-1-(3,4-dichlorophenyl)prop-2-en-1-one [C23H14OCl2] is synthesized and its crystal structure is determined by single X-ray diffraction. There exist two molecules in the asymmetric unit. The dihedral angle between the benzene and anthracene moiety of the molecule A and B is 86.51(12)° and 76.42(13)°, respectively. No classical hydrogen bonds are observed and only van der Waals forces stabilize the crystal packing.

Novel heterocyclic thiosemicarbazones derivatives as colorimetric and "turn on" fluorescent sensors for fluoride anion sensing employing hydrogen bonding.

PubMed

Ashok Kumar, S L; Saravana Kumar, M; Sreeja, P B; Sreekanth, A

2013-09-01

Two novel heterocyclic thiosemicarbazone derivatives have been synthesized, and characterized, by means of spectroscopic and single crystal X-ray diffraction methods. Their chromophoric-fluorogenic response towards anions in competing solvent dimethyl sulfoxide (DMSO) was studied. The receptor shows selective recognition towards fluoride anion. The binding affinity of the receptors with fluoride anion was calculated using UV-visible and fluorescence spectroscopic techniques. Copyright © 2013 Elsevier B.V. All rights reserved.

Crystal structure and density of helium to 232 kbar

NASA Technical Reports Server (NTRS)

Mao, H. K.; Wu, Y.; Jephcoat, A. P.; Hemley, R. J.; Bell, P. M.; Bassett, W. A.

1988-01-01

The properties of helium and hydrogen at high pressure are topics of great interest to the understanding of planetary interiors. These materials constitute 95 percent of the entire solar system. A technique was presented for the measurement of X-ray diffraction from single-crystals of low-Z condenses gases in a diamond-anvil cell at high pressure. The first such single-crystal X-ray diffraction measurements on solid hydrogen to 26.5 GPa were presented. The application of this technique to the problem of the crystal structure, equation of state, and phase diagram of solid helium is reported. Crucial for X-ray diffraction studies of these materials is the use of a synchrotron radiation source which provides high brillance, narrow collimation of the incident and diffracted X-ray beams to reduce the background noise, and energy-dispersive diffraction techniques with polychromatic (white) radiation, which provides high detection efficiency.

Structural investigation of porcine stomach mucin by X-ray fiber diffraction and homology modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Veluraja, K., E-mail: veluraja@msuniv.ac.in; Vennila, K.N.; Umamakeshvari, K.

Research highlights: {yields} Techniques to get oriented mucin fibre. {yields} X-ray fibre diffraction pattern for mucin. {yields} Molecular modeling of mucin based on X-ray fibre diffraction pattern. -- Abstract: The basic understanding of the three dimensional structure of mucin is essential to understand its physiological function. Technology has been developed to achieve orientated porcine stomach mucin molecules. X-ray fiber diffraction of partially orientated porcine stomach mucin molecules show d-spacing signals at 2.99, 4.06, 4.22, 4.7, 5.37 and 6.5 A. The high intense d-spacing signal at 4.22 A is attributed to the antiparallel {beta}-sheet structure identified in the fraction of themore » homology modeled mucin molecule (amino acid residues 800-980) using Nidogen-Laminin complex structure as a template. The X-ray fiber diffraction signal at 6.5 A reveals partial organization of oligosaccharides in porcine stomach mucin. This partial structure of mucin will be helpful in establishing a three dimensional structure for the whole mucin molecule.« less

A nearly on-axis spectroscopic system for simultaneously measuring UV-visible absorption and X-ray diffraction in the SPring-8 structural genomics beamline.

PubMed

Sakaguchi, Miyuki; Kimura, Tetsunari; Nishida, Takuma; Tosha, Takehiko; Sugimoto, Hiroshi; Yamaguchi, Yoshihiro; Yanagisawa, Sachiko; Ueno, Go; Murakami, Hironori; Ago, Hideo; Yamamoto, Masaki; Ogura, Takashi; Shiro, Yoshitsugu; Kubo, Minoru

2016-01-01

UV-visible absorption spectroscopy is useful for probing the electronic and structural changes of protein active sites, and thus the on-line combination of X-ray diffraction and spectroscopic analysis is increasingly being applied. Herein, a novel absorption spectrometer was developed at SPring-8 BL26B2 with a nearly on-axis geometry between the X-ray and optical axes. A small prism mirror was placed near the X-ray beamstop to pass the light only 2° off the X-ray beam, enabling spectroscopic analysis of the X-ray-exposed volume of a crystal during X-ray diffraction data collection. The spectrometer was applied to NO reductase, a heme enzyme that catalyzes NO reduction to N2O. Radiation damage to the heme was monitored in real time during X-ray irradiation by evaluating the absorption spectral changes. Moreover, NO binding to the heme was probed via caged NO photolysis with UV light, demonstrating the extended capability of the spectrometer for intermediate analysis.

Investigating the Effects of Low Temperature Annealing of Amorphous Corrosion Resistant Alloys.

DTIC Science & Technology

1980-11-01

Ray Diffraction.................................................... 6 Differential Scanning Calorimetry....................................... 9...17 LIST OF FIGURES Figure 1. X- Ray Diffraction Results From Fe32Ni 36Cr 4P 2 B Annealed for One Hour at...Various Temperatures (Cr Ka Radiation) ................................. 7 Figure 2. X- Ray Diffraction Results From FeU2NiaeCr14SieB Annealed for One

Metal–Metal Bonding in Uranium–Group 10 Complexes

PubMed Central

2016-01-01

Heterobimetallic complexes containing short uranium–group 10 metal bonds have been prepared from monometallic IUIV(OArP-κ2O,P)3 (2) {[ArPO]− = 2-tert-butyl-4-methyl-6-(diphenylphosphino)phenolate}. The U–M bond in IUIV(μ-OArP-1κ1O,2κ1P)3M0, M = Ni (3–Ni), Pd (3–Pd), and Pt (3–Pt), has been investigated by experimental and DFT computational methods. Comparisons of 3–Ni with two further U–Ni complexes XUIV(μ-OArP-1κ1O,2κ1P)3Ni0, X = Me3SiO (4) and F (5), was also possible via iodide substitution. All complexes were characterized by variable-temperature NMR spectroscopy, electrochemistry, and single crystal X-ray diffraction. The U–M bonds are significantly shorter than any other crystallographically characterized d–f-block bimetallic, even though the ligand flexes to allow a variable U–M separation. Excellent agreement is found between the experimental and computed structures for 3–Ni and 3–Pd. Natural population analysis and natural localized molecular orbital (NLMO) compositions indicate that U employs both 5f and 6d orbitals in covalent bonding to a significant extent. Quantum theory of atoms-in-molecules analysis reveals U–M bond critical point properties typical of metallic bonding and a larger delocalization index (bond order) for the less polar U–Ni bond than U–Pd. Electrochemical studies agree with the computational analyses and the X-ray structural data for the U–X adducts 3–Ni, 4, and 5. The data show a trend in uranium–metal bond strength that decreases from 3–Ni down to 3–Pt and suggest that exchanging the iodide for a fluoride strengthens the metal–metal bond. Despite short U–TM (transition metal) distances, four other computational approaches also suggest low U–TM bond orders, reflecting highly transition metal localized valence NLMOs. These are more so for 3–Pd than 3–Ni, consistent with slightly larger U–TM bond orders in the latter. Computational studies of the model systems (PH3)3MU(OH)3I (M = Ni, Pd) reveal longer and weaker unsupported U–TM bonds vs 3. PMID:26942560

Evidence from x-ray and neutron powder diffraction patterns that the so-called icosahedral and decagonal quasicrystals of MnAl(6) and other alloys are twinned cubic crystals.

PubMed

Pauling, L

1987-06-01

It is shown that the x-ray powder diffraction patterns of rapidly quenched MnAl(6) and Mg(32)(Al,Zn)(49) and the neutron powder diffraction pattern of MnAl(6) are compatible with the proposed 820-atom primitive cubic structure [Pauling, L. (1987) Phys. Rev. Lett. 58, 365-368]. The values found for the edge of the unit cube are 23.365 A (x-ray) and 23.416 A (neutron) for MnAl(6) and 24.313 A (x-ray) for Mg(32)(Al,Zn)(49).

Evidence from x-ray and neutron powder diffraction patterns that the so-called icosahedral and decagonal quasicrystals of MnAl6 and other alloys are twinned cubic crystals

PubMed Central

Pauling, Linus

1987-01-01

It is shown that the x-ray powder diffraction patterns of rapidly quenched MnAl6 and Mg32(Al,Zn)49 and the neutron powder diffraction pattern of MnAl6 are compatible with the proposed 820-atom primitive cubic structure [Pauling, L. (1987) Phys. Rev. Lett. 58, 365-368]. The values found for the edge of the unit cube are 23.365 Å (x-ray) and 23.416 Å (neutron) for MnAl6 and 24.313 Å (x-ray) for Mg32(Al,Zn)49. PMID:16593841

High-energy X-ray diffraction using the Pixium 4700 flat-panel detector.

PubMed

Daniels, J E; Drakopoulos, M

2009-07-01

The Pixium 4700 detector represents a significant step forward in detector technology for high-energy X-ray diffraction. The detector design is based on digital flat-panel technology, combining an amorphous Si panel with a CsI scintillator. The detector has a useful pixel array of 1910 x 2480 pixels with a pixel size of 154 microm x 154 microm, and thus it covers an effective area of 294 mm x 379 mm. Designed for medical imaging, the detector has good efficiency at high X-ray energies. Furthermore, it is capable of acquiring sequences of images at 7.5 frames per second in full image mode, and up to 60 frames per second in binned region of interest modes. Here, the basic properties of this detector applied to high-energy X-ray diffraction are presented. Quantitative comparisons with a widespread high-energy detector, the MAR345 image plate scanner, are shown. Other properties of the Pixium 4700 detector, including a narrow point-spread function and distortion-free image, allows for the acquisition of high-quality diffraction data at high X-ray energies. In addition, high frame rates and shutterless operation open new experimental possibilities. Also provided are the necessary data for the correction of images collected using the Pixium 4700 for diffraction purposes.

Indium local geometry in In-Sb-Te thin films using XANES and DFT calculations

NASA Astrophysics Data System (ADS)

Bilovol, V.; Gil Rebaza, A. V.; Mudarra Navarro, A. M.; Errico, L.; Fontana, M.; Arcondo, B.

2017-12-01

In-Sb-Te when is a thin film presents a huge difference in its electrical resistivity when transform from the amorphous (insulating) to the crystalline (conducting) phase. This property made this system one of the main phase-change materials used in the data storage industry. The change in the electrical conductivity is probably associated to a change in the bonding geometry of some of its constituents. To explore this point, we present in this work an study of the bonding geometry of In atoms in In-Sb-Te films by means of In K-edge X-ray absorption near edge structure (XANES) spectroscopy using synchrotron radiation in both as deposited (amorphous) and crystalline thin films obtained as a result of resistance (R) vs temperature (T) measurements. Comparison of the XANES spectra obtained for ternary amorphous films and binary crystalline reference films suggests that in amorphous films the bonding geometry of In atoms is tetrahedral-like. After the thermal annealing has been carried out the differences in the XANES spectra of the as deposited and the annealed films indicate that the bonding geometry of In atoms changes. Based on X-ray diffraction results and ab initio calculations in the framework of the Density Functional Theory (DFT) we show that the new coordination geometry is associated with a tendency of In atoms towards octahedral-like.

Crystallization and preliminary X-ray diffraction analysis of a chitin-binding domain of hyperthermophilic chitinase from Pyrococcus furiosus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakamura, Tsutomu; Ishikawa, Kazuhiko; Hagihara, Yoshihisa

The expression, purification and preliminary X-ray diffraction studies of a chitin-binding domain of the chitinase from P. furiosus are reported. The crystallization and preliminary X-ray diffraction analysis of the chitin-binding domain of chitinase from a hyperthermophilic archaeon, Pyrococcus furiosus, are reported. The recombinant protein was prepared using an Escherichia coli overexpression system and was crystallized by the hanging-drop vapour-diffusion method. An X-ray diffraction data set was collected to 1.70 Å resolution. The crystal belonged to space group P4{sub 3}2{sub 1}2 or P4{sub 1}2{sub 1}2. The unit-cell parameters were determined to be a = b = 48.8, c = 85.0 Å.

Long-Wavelength X-Ray Diffraction and Its Applications in Macromolecular Crystallography.

PubMed

Weiss, Manfred S

2017-01-01

For many years, diffraction experiments in macromolecular crystallography at X-ray wavelengths longer than that of Cu-K α (1.54 Å) have been largely underappreciated. Effects caused by increased X-ray absorption result in the fact that these experiments are more difficult than the standard diffraction experiments at short wavelengths. However, due to the also increased anomalous scattering of many biologically relevant atoms, important additional structural information can be obtained. This information, in turn, can be used for phase determination, for substructure identification, in molecular replacement approaches, as well as in structure refinement. This chapter reviews the possibilities and the difficulties associated with such experiments, and it provides a short description of two macromolecular crystallography synchrotron beam lines dedicated to long-wavelength X-ray diffraction experiments.

Data processing software suite SITENNO for coherent X-ray diffraction imaging using the X-ray free-electron laser SACLA.

PubMed

Sekiguchi, Yuki; Oroguchi, Tomotaka; Takayama, Yuki; Nakasako, Masayoshi

2014-05-01

Coherent X-ray diffraction imaging is a promising technique for visualizing the structures of non-crystalline particles with dimensions of micrometers to sub-micrometers. Recently, X-ray free-electron laser sources have enabled efficient experiments in the `diffraction before destruction' scheme. Diffraction experiments have been conducted at SPring-8 Angstrom Compact free-electron LAser (SACLA) using the custom-made diffraction apparatus KOTOBUKI-1 and two multiport CCD detectors. In the experiments, ten thousands of single-shot diffraction patterns can be collected within several hours. Then, diffraction patterns with significant levels of intensity suitable for structural analysis must be found, direct-beam positions in diffraction patterns determined, diffraction patterns from the two CCD detectors merged, and phase-retrieval calculations for structural analyses performed. A software suite named SITENNO has been developed to semi-automatically apply the four-step processing to a huge number of diffraction data. Here, details of the algorithm used in the suite are described and the performance for approximately 9000 diffraction patterns collected from cuboid-shaped copper oxide particles reported. Using the SITENNO suite, it is possible to conduct experiments with data processing immediately after the data collection, and to characterize the size distribution and internal structures of the non-crystalline particles.

Data processing software suite SITENNO for coherent X-ray diffraction imaging using the X-ray free-electron laser SACLA

PubMed Central

Sekiguchi, Yuki; Oroguchi, Tomotaka; Takayama, Yuki; Nakasako, Masayoshi

2014-01-01

Coherent X-ray diffraction imaging is a promising technique for visualizing the structures of non-crystalline particles with dimensions of micrometers to sub-micrometers. Recently, X-ray free-electron laser sources have enabled efficient experiments in the ‘diffraction before destruction’ scheme. Diffraction experiments have been conducted at SPring-8 Angstrom Compact free-electron LAser (SACLA) using the custom-made diffraction apparatus KOTOBUKI-1 and two multiport CCD detectors. In the experiments, ten thousands of single-shot diffraction patterns can be collected within several hours. Then, diffraction patterns with significant levels of intensity suitable for structural analysis must be found, direct-beam positions in diffraction patterns determined, diffraction patterns from the two CCD detectors merged, and phase-retrieval calculations for structural analyses performed. A software suite named SITENNO has been developed to semi-automatically apply the four-step processing to a huge number of diffraction data. Here, details of the algorithm used in the suite are described and the performance for approximately 9000 diffraction patterns collected from cuboid-shaped copper oxide particles reported. Using the SITENNO suite, it is possible to conduct experiments with data processing immediately after the data collection, and to characterize the size distribution and internal structures of the non-crystalline particles. PMID:24763651

The crystallization behavior of amorphous Ge2Sb2Te5 films induced by a multi-pulsed nanosecond laser

NASA Astrophysics Data System (ADS)

Fan, T.; Liu, F. R.; Li, W. Q.; Guo, J. C.; Wang, Y. H.; Sun, N. X.; Liu, F.

2017-09-01

In this paper, accumulated crystallization of amorphous Ge2Sb2Te5 (a-GST) films induced by a multi-pulsed nanosecond (ns) excimer laser was investigated by x-ray diffraction (XRD), atomic force microscopy, field-emission scanning electron microscopy, x-ray photoelectron spectroscopy (XPS) and a spectrophotometer. XRD analyses revealed that detectable crystallization was firstly observed in the preferred orientation (200), followed by the orientations (220) and (111) after two pulses. Optical contrast, determined by crystallinity as well as surface roughness, was found to retain a linear relation within the first three pulses. A layered growth mechanism from the top surface to the interior of a-GST films was used to explain the crystallization behavior induced by the multi-pulse ns laser. XPS analyses for bond rearrangement and electronic structure further suggested that the crystallization process was performed by generating new bonds of Ge-Te and Sb-Te after laser irradiations. This paper presents the potential of multi-level devices and tunable thermal emitters based on controllable crystallization of phase-change materials.

Ligand exchange synthesis of organometallic Rh nanoparticles and application in explosive sensing

NASA Astrophysics Data System (ADS)

Srivastav, Amit K.; Agrawal, Bhavesh; Swami, Bhavya; Agrawal, Yadvendra K.; Maity, Prasenjit

2017-06-01

Alkyne {phenyl acetylene (PA) and 9-ethynylphenanthrene (EPT)}-ligated Rh nanoparticles ( 1 and 2, respectively) with mean diameter of 1.5 ± 0.2 nm were synthesized via a facile and high-yield biphasic ligand exchange protocol using similar sized ethylene glycol (EG)-stabilized Rh nanoparticles as precursors (EG:Rh). The synthesized organometallic Rh nanoparticles were convincingly characterized using several spectroscopic and microscopic techniques, e.g., Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H NMR), optical absorption spectroscopy (UV-Vis), photoluminescence spectroscopy (PL), powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscope (TEM). We propose that the syntheses mechanism relies on catalytic acetylenic (≡C-H, carbon-hydrogen) bond breaking by EG:Rh followed by strong metal-carbon bond formation with a vinyldiene (>C═C═M) motif. The obtained 1 and 2 showed luminescence property, which arises from ligand structure through intraparticle conjugation. Electron-rich phenanthrene-ligated Rh nanoparticles ( 2) showed good sensing performance for detection of electron deficient nitro-aromatic explosive molecules (NA) in solution phase through luminescence quenching method.

Neutrally Charged Gas/Liquid Interface by a Catanionic Langmuir Monolayer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vaknin, David; Bu, Wei

Surface-sensitive synchrotron X-ray scattering and spectroscopic experiments were performed to explore the characteristics of Langmuir monolayers of oppositely charged mixed amphiphiles. A premixed (molar 1:1 stearic acid/stearylamine) solution was spread as a monolayer at the gas/liquid interface on pure water and on mono- and divalent salt solutions, revealing that the negatively charged carboxyl groups and positively charged amine groups are miscible into one another and tend to bond together to form a nearly neutral surface. Similar control experiments on pure stearic acid (SA) and stearylamine (ST) were also conducted for comparison. Due to the strong bonding, hexagonal structures in smallmore » domains with acyl-chains normal to the liquid surface are formed at zero surface pressures, that is, at molecular areas much larger than those of the densely packed acyl chains. In-plane X-ray diffraction indicates that the catanionic surface is highly ordered and modifies the structure of the water surface and thus can serve as a model system for interactions of an amino acid template with solutes.« less

Spectroscopic and Thermal Behavior of Chromium Soaps

NASA Astrophysics Data System (ADS)

Mehrotra, K. N.; Jain, Mamta

1996-02-01

The physicochemical characteristics of chromium soaps (myristate and stearate) were investigated in the solid state (thermal, X-ray, and IR measurements) and in solutions (spectrophotometric measurements). The thermal measurements showed that the decomposition of chromium soaps is a two-step process. The soap decomposed into chromium oxycarboxylate, ketone, and carbon dioxide in the first step and the intermediate oxycarboxylate underwent further decomposition to chromium trioxide in the second step. The results showed that the second step is kinetically of zero order and the values of energy of activation for the first and second steps lie in the ranges 6-7 and 17-18 kcal mol-1, respectively. The X-ray diffraction results showed that these soaps possess double-layer structure with molecular axes slightly inclined to the basal plane. The infrared results revealed that the fatty acids exist with dimeric structure through hydrogen bonding between two molecules of fatty acids whereas the metal-to-oxygen bonds in chromium soaps are not purely ionic but possess considerable covalent character. The results of spectrophotometric measurements also confirmed the somewhat covalent nature of chromium soaps in solutions in dichloromethane.

Local atomic structure inheritance in Ag{sub 50}Sn{sub 50} melt

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bai, Yanwen; Bian, Xiufang, E-mail: xfbian@sdu.edu.cn; Qin, Jingyu

2014-01-28

Local structure inheritance signatures were observed during the alloying process of the Ag{sub 50}Sn{sub 50} melt, using high-temperature X-ray diffraction and ab initio molecular dynamics simulations. The coordination number N{sub m} around Ag atom is similar in the alloy and in pure Ag melts (N{sub m} ∼ 10), while, during the alloying process, the local structure around Sn atoms rearranges. Sn-Sn covalent bonds were substituted by Ag-Sn chemical bonds, and the total coordination number around Sn increases by about 70% as compared with those in the pure Sn melt. Changes in the electronic structure of the alloy have been studied by Agmore » and Sn K-edge X-ray absorption spectroscopy, as well as by calculations of the partial density of states. We propose that a leading mechanism for local structure inheritance in Ag{sub 50}Sn{sub 50} is due to s-p dehybridization of Sn and to the interplay between Sn-s and Ag-d electrons.« less

Synthesis, spectral characterization, thermal behaviour, antibacterial activity and DFT calculation on N‧-[bis(methylsulfanyl) methylene]-2-hydroxybenzohydrazide and N‧-(4-methoxy benzoyl)-hydrazinecarbodithioic acid ethyl ester

NASA Astrophysics Data System (ADS)

Bharty, M. K.; Dani, R. K.; Kushawaha, S. K.; Prakash, Om; Singh, Ranjan K.; Sharma, V. K.; Kharwar, R. N.; Singh, N. K.

2015-06-01

Two new compounds N‧-[bis(methylsulfanyl) methylene]-2-hydroxybenzohydrazide {Hbmshb (1)} and N‧-(4-methoxy benzoyl)-hydrazinecarbodithioic acid ethyl ester {H2mbhce (2)} have been synthesized and characterized with the aid of elemental analyses, IR, NMR and single crystal X-ray diffraction data. Compounds 1 and 2 crystallize in orthorhombic and monoclinic systems with space group Pna21 and P21/n, respectively. Inter and intra molecular hydrogen bonding link two molecules and provide linear chain structure. In addition to this, compound 2 is stabilized by CH⋯π and NH⋯π interactions. Molecular geometry from X-ray analysis, geometry optimization, charge distribution, bond analysis, frontier molecular orbital (FMO) analysis and non-linear optical (NLO) effects have been performed using the density functional theory (DFT) with the B3LYP functional. The bioefficacy of compounds has been examined against the growth of bacteria to evaluate their anti-microbial potential. Compounds 1 and 2 are thermally stable and show NLO behaviour better than the urea crystal.

Whisker growth of l-menthol in coexistence with various excipients.

PubMed

Yuasa, H; Ooi, M; Takashima, Y; Kanaya, Y

2000-08-10

The purpose of the present study was to clarify the mechanism for l-menthol whisker growth. l-Menthol was mixed with an excipient, and the interaction was examined by IR measurement, thermal analysis and powder X-ray diffraction. Then we examined the involvement of the capillary condensation using the pore size distribution measurement. By mixing l-menthol with an excipient with whisker growth, the hydroxyl group stretching band of l-menthol was shifted to the higher wavenumber in the IR spectrum, the melting point and heat of fusion of l-menthol became lower in the thermal analysis, and the diffraction intensity of l-menthol became lower in the powder X-ray diffraction. The excipients with whisker growth showed the tendency to have the meso-pore involved in the capillary condensation in the pore size distribution measurement. From the above results, the whisker growth mechanism is considered as follows. When l-menthol was mixed with an excipient with whisker growth, the crystallinity of l-menthol was lowered and the vapor pressure was increased by the interaction mainly consisting of the hydrogen bond. The generated l-menthol vapor entered meso-pore, the saturated vapor pressure was lowered by the capillary condensation, and the nucleation occurred. The vapor was further supplied, generating the growth of whisker.

A combined experimental and in silico characterization to highlight additional structural features and properties of a potentially new drug

NASA Astrophysics Data System (ADS)

Bastos, Isadora T. S.; Costa, Fanny N.; Silva, Tiago F.; Barreiro, Eliezer J.; Lima, Lídia M.; Braz, Delson; Lombardo, Giuseppe M.; Punzo, Francesco; Ferreira, Fabio F.; Barroso, Regina C.

2017-10-01

LASSBio-1755 is a new cycloalkyl-N-acylhydrazone parent compound designed for the development of derivatives with antinociceptive and anti-inflammatory activities. Although single crystal X-ray diffraction has been considered as the golden standard in structure determination, we successfully used X-ray powder diffraction data in the structural determination of new synthesized compounds, in order to overcome the bottle-neck due to the difficulties experienced in harvesting good quality single crystals of the compounds. We therefore unequivocally assigned the relative configuration (E) to the imine double bond and a s-cis conformation of the amide function of the N-acylhydrazone compound. These features are confirmed by a computational analysis performed on the basis of molecular dynamics calculations, which are extended not only to the structural characteristics but also to the analysis of the anisotropic atomic displacement parameters, a further information - missed in a typical powder diffraction analysis. The so inferred data were used to perform additional cycles of refinement and eventually generate a new cif file with additional physical information. Furthermore, crystal morphology prediction was performed, which is in agreement with the experimental images acquired by scanning electron microscopy, thus providing useful information on possible alternative paths for better crystallization strategies.

Spectroscopic imaging, diffraction, and holography with x-ray photoemission

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1992-02-01

X-ray probes are capable of determining the spatial structure of an atom in a specific chemical state, over length scales from about a micron all the way down to atomic resolution. Examples of these probes include photoemission microscopy, energy-dependent photoemission diffraction, photoelectron holography, and X-ray absorption microspectroscopy. Although the method of image formation, chemical-state sensitivity, and length scales can be very different, these X-ray techniques share a common goal of combining a capability for structure determination with chemical-state specificity. This workshop will address recent advances in holographic, diffraction, and direct imaging techniques using X-ray photoemission on both theoretical and experimentalmore » fronts. A particular emphasis will be on novel structure determinations with atomic resolution using photoelectrons.« less

An instrument for in situ coherent x-ray studies of metal-organic vapor phase epitaxy of III-nitrides.

PubMed

Ju, Guangxu; Highland, Matthew J; Yanguas-Gil, Angel; Thompson, Carol; Eastman, Jeffrey A; Zhou, Hua; Brennan, Sean M; Stephenson, G Brian; Fuoss, Paul H

2017-03-01

We describe an instrument that exploits the ongoing revolution in synchrotron sources, optics, and detectors to enable in situ studies of metal-organic vapor phase epitaxy (MOVPE) growth of III-nitride materials using coherent x-ray methods. The system includes high-resolution positioning of the sample and detector including full rotations, an x-ray transparent chamber wall for incident and diffracted beam access over a wide angular range, and minimal thermal sample motion, giving the sub-micron positional stability and reproducibility needed for coherent x-ray studies. The instrument enables surface x-ray photon correlation spectroscopy, microbeam diffraction, and coherent diffraction imaging of atomic-scale surface and film structure and dynamics during growth, to provide fundamental understanding of MOVPE processes.

An instrument for in situ coherent x-ray studies of metal-organic vapor phase epitaxy of III-nitrides

NASA Astrophysics Data System (ADS)

Ju, Guangxu; Highland, Matthew J.; Yanguas-Gil, Angel; Thompson, Carol; Eastman, Jeffrey A.; Zhou, Hua; Brennan, Sean M.; Stephenson, G. Brian; Fuoss, Paul H.

2017-03-01

We describe an instrument that exploits the ongoing revolution in synchrotron sources, optics, and detectors to enable in situ studies of metal-organic vapor phase epitaxy (MOVPE) growth of III-nitride materials using coherent x-ray methods. The system includes high-resolution positioning of the sample and detector including full rotations, an x-ray transparent chamber wall for incident and diffracted beam access over a wide angular range, and minimal thermal sample motion, giving the sub-micron positional stability and reproducibility needed for coherent x-ray studies. The instrument enables surface x-ray photon correlation spectroscopy, microbeam diffraction, and coherent diffraction imaging of atomic-scale surface and film structure and dynamics during growth, to provide fundamental understanding of MOVPE processes.

Hydrothermal Diamond Anvil Cell (HDAC): From Visual Observation to X-ray Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

Bassett, W. A.; Mibe, K.

2006-05-01

A fluid sample contained in a Re gasket between two diamond anvils can be subjected to pressures up to 2.5 GPa and temperatures up to 1200°C in a resistively heated hydrothermal diamond anvil cell (HDAC). Thermocouples are used to measure temperature. The constant-volume sample chamber permits isochoric measurements that can be used to determine pressure from the equation of state of H2O and to map phases and properties in P-T space. A movie of reactions between K-feldspar and water up to 2.5 GPa and 880°C illustrates the use of visual observations for mapping coexisting solution, melt, and solid phases. X-ray absorption spectroscopy of ZnBr2 in solution up to 500°C and 500 MPa shows hydrogen bond breaking in the hydration shells of the ZnBr42- and Br- ions with increasing temperature. In other studies the stability field of ikaite (CaCO3·6H2O) has been mapped by visual observation and Raman spectroscopy; the phases of montmorillonite have been mapped by X-ray diffraction; and the leaching of Pb from zircon has been measured by X-ray microprobe.

Large Area Atomically Flat Surfaces via Exfoliation of Bulk Bi 2Se 3 Single Crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Melamed, Celeste L.; Ortiz, Brenden R.; Gorai, Prashun

In this paper, we present an exfoliation method that produces cm 2-area atomically flat surfaces from bulk layered single crystals, with broad applications such as for the formation of lateral heterostructures and for use as substrates for van der Waals epitaxy. Single crystals of Bi 2Se 3 were grown using the Bridgman method and examined with X-ray reciprocal space maps, Auger spectroscopy, low-energy electron diffraction, and X-ray photoelectron spectroscopy. An indium-bonding exfoliation technique was developed that produces multiple ~100 um thick atomically flat, macroscopic (>1 cm 2) slabs from each Bi 2Se 3 source crystal. Two-dimensional X-ray diffraction and reciprocalmore » space maps confirm the high crystalline quality of the exfoliated surfaces. Atomic force microscopy reveals that the exfoliated surfaces have an average root-mean-square (RMS) roughness of ~0.04 nm across 400 μm 2 scans and an average terrace width of 70 um between step edges. First-principles calculations reveal exfoliation energies of Bi 2Se 3 and a number of other layered compounds, which demonstrate relevance of our method across the field of 2D materials. While many potential applications exist, excellent lattice matching with the III-V alloy space suggests immediate potential for the use of these exfoliated layered materials as epitaxial substrates for photovoltaic development.« less

Large Area Atomically Flat Surfaces via Exfoliation of Bulk Bi 2Se 3 Single Crystals

DOE PAGES

Melamed, Celeste L.; Ortiz, Brenden R.; Gorai, Prashun; ...

2017-09-12

In this paper, we present an exfoliation method that produces cm 2-area atomically flat surfaces from bulk layered single crystals, with broad applications such as for the formation of lateral heterostructures and for use as substrates for van der Waals epitaxy. Single crystals of Bi 2Se 3 were grown using the Bridgman method and examined with X-ray reciprocal space maps, Auger spectroscopy, low-energy electron diffraction, and X-ray photoelectron spectroscopy. An indium-bonding exfoliation technique was developed that produces multiple ~100 um thick atomically flat, macroscopic (>1 cm 2) slabs from each Bi 2Se 3 source crystal. Two-dimensional X-ray diffraction and reciprocalmore » space maps confirm the high crystalline quality of the exfoliated surfaces. Atomic force microscopy reveals that the exfoliated surfaces have an average root-mean-square (RMS) roughness of ~0.04 nm across 400 μm 2 scans and an average terrace width of 70 um between step edges. First-principles calculations reveal exfoliation energies of Bi 2Se 3 and a number of other layered compounds, which demonstrate relevance of our method across the field of 2D materials. While many potential applications exist, excellent lattice matching with the III-V alloy space suggests immediate potential for the use of these exfoliated layered materials as epitaxial substrates for photovoltaic development.« less

On the nature and origin of the oxalate package in Solanum sisymbriifolium anthers.

PubMed

Burrieza, Hernán Pablo; López-Fernández, María Paula; Láinez, Verónica; Montenegro, Teresita; Maldonado, Sara

2010-11-01

This is a detailed study carried out in Solanum sisymbriifolium Lam. on the development of the circular cell cluster (CCC) during crystal deposition, as well as the composition of the crystals. Light microscopy and scanning and transmission electron microscopy (TEM) were used to characterize tissue throughout anther development. Energy dispersive X-ray analysis (EDAX) allowed the determination of the elemental composition of crystals that form in the CCC region, and infrared and x-ray diffraction analysis were used to specify the crystal salt composition. TEM analysis revealed that the crystals originated simultaneously within the vacuoles in association with a paracrystalline protein. Prior to the appearance of protein within vacuoles, protein paracrystals were visible in both rough endoplasmic reticulum and vesicles with ribosomes on their membranes. In vacuoles, paracrystals constitute nucleation sites for druse crystals formation. EDAX revealed that C, O, and Ca were the main elements, and K, Cl, Mg, P, S, and Si, the minor elements. X-ray powder diffraction of crystals detected the predominant presence of calcium oxalate, but also vestiges of calcite, quartz, and sylvite. The calcium oxalate coexisted in the three chemical forms, that is, whewellite, weddellite, and caoxite. Infrared spectrophotometry identified bands that characterize O-C-O, H-O, C-H bonds, all of calcium oxalate, and Si-O-Si, of quartz. These results were compared with studies of anthers carried out in other Solanaceae genera.

Combined X-ray and neutron fibre diffraction studies of biological and synthetic polymers

NASA Astrophysics Data System (ADS)

Parrot, I. M.; Urban, V.; Gardner, K. H.; Forsyth, V. T.

2005-08-01

The fibrous state is a natural one for polymer molecules which tend to assume regular helical conformations rather than the globular structures characteristic of many proteins. Fibre diffraction therefore has broad application to the study of a wide range of biological and synthetic polymers. The purpose of this paper is to illustrate the general scope of the method and in particular to demonstrate the impact of a combined approach involving both X-ray and neutron diffraction methods. While the flux of modern X-ray synchrotron radiation sources allows high quality datasets to be recorded with good resolution within a very short space of time, neutron studies can provide unique information through the ability to locate hydrogen or deuterium atoms that are often difficult or impossible to locate using X-ray methods. Furthermore, neutron fibre diffraction methods can, through the ability to selectively label specific parts of a structure, be used to highlight novel aspects of polymer structure that can not be studied using X-rays. Two examples are given. The first describes X-ray and neutron diffraction studies of conformational transitions in DNA. The second describes structural studies of the synthetic high-performance polymer poly(p-phenylene terephthalamide) (PPTA), known commercially as Kevlar® or Twaron®.

Conceptual Design for Time-Resolved X-ray Diffraction in a Single Laser-Driven Compression Experiment

NASA Astrophysics Data System (ADS)

Benedetti, Laura Robin; Eggert, J. H.; Kilkenny, J. D.; Bradley, D. K.; Bell, P. M.; Palmer, N. E.; Rygg, J. R.; Boehly, T. R.; Collins, G. W.; Sorce, C.

2017-06-01

Since X-ray diffraction is the most definitive method for identifying crystalline phases of a material, it is an important technique for probing high-energy-density materials during laser-driven compression experiments. We are developing a design for collecting several x-ray diffraction datasets during a single laser-driven experiment, with a goal of achieving temporal resolution better than 1ns. The design combines x-ray streak cameras, for a continuous temporal record of diffraction, with fast x-ray imagers, to collect several diffraction patterns with sufficient solid angle range and resolution to identify crystalline texture. Preliminary experiments will be conducted at the Omega laser and then implemented at the National Ignition Facility. We will describe the status of the conceptual design, highlighting tradeoffs in the design process. We will also discuss the technical issues that must be addressed in order to develop a successful experimental platform. These include: Facility-specific geometric constraints such as unconverted laser light and target alignment; EMP issues when electronic diagnostics are close to the target; X-ray source requirements; and detector capabilities. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344, LLNL-ABS-725146.

The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3BH 3)(H 2) x(x = 1.5) compound

DOE PAGES

Lin, Yu; Welchman, Evan; Thonhauser, Timo; ...

2017-03-15

Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH 3BH 3)(H 2) x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH 3BH 3) in an environment with an excess of molecular hydrogen (H 2). This compound can store a total of 26.8 wt% hydrogen, both as molecular hydrogen and chemically bonded hydrogen in AB, making it one of the most hydrogen-rich solids currently known. The new compound possesses a layered AB structure where additional H 2 molecules reside in channels created through the weavingmore » of AB layers. The unconventional dihydrogen bonding network of the new compound is significantly modified from its parent AB phase and contains H•••H contacts between adjacent AB molecules and between AB and H 2 molecules. H–H can be either a proton donor or a proton acceptor that forms new types of dihydrogen bonding with the host AB molecules, which are depicted as H–H•••H–B or H–H•••H–N, respectively. Furthermore, this study not only demonstrates the strategy and the promise of using pressure for new material synthesis, but also unleashes the power of combining experiments and ab initio calculations for elucidating novel structures and unusual bonding configurations in dense low-Z materials.« less

The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3BH 3)(H 2) x(x = 1.5) compound

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yu; Welchman, Evan; Thonhauser, Timo

Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH 3BH 3)(H 2) x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH 3BH 3) in an environment with an excess of molecular hydrogen (H 2). This compound can store a total of 26.8 wt% hydrogen, both as molecular hydrogen and chemically bonded hydrogen in AB, making it one of the most hydrogen-rich solids currently known. The new compound possesses a layered AB structure where additional H 2 molecules reside in channels created through the weavingmore » of AB layers. The unconventional dihydrogen bonding network of the new compound is significantly modified from its parent AB phase and contains H•••H contacts between adjacent AB molecules and between AB and H 2 molecules. H–H can be either a proton donor or a proton acceptor that forms new types of dihydrogen bonding with the host AB molecules, which are depicted as H–H•••H–B or H–H•••H–N, respectively. Furthermore, this study not only demonstrates the strategy and the promise of using pressure for new material synthesis, but also unleashes the power of combining experiments and ab initio calculations for elucidating novel structures and unusual bonding configurations in dense low-Z materials.« less

IDATEN and G-SITENNO: GUI-assisted software for coherent X-ray diffraction imaging experiments and data analyses at SACLA.

PubMed

Sekiguchi, Yuki; Yamamoto, Masaki; Oroguchi, Tomotaka; Takayama, Yuki; Suzuki, Shigeyuki; Nakasako, Masayoshi

2014-11-01

Using our custom-made diffraction apparatus KOTOBUKI-1 and two multiport CCD detectors, cryogenic coherent X-ray diffraction imaging experiments have been undertaken at the SPring-8 Angstrom Compact free electron LAser (SACLA) facility. To efficiently perform experiments and data processing, two software suites with user-friendly graphical user interfaces have been developed. The first is a program suite named IDATEN, which was developed to easily conduct four procedures during experiments: aligning KOTOBUKI-1, loading a flash-cooled sample into the cryogenic goniometer stage inside the vacuum chamber of KOTOBUKI-1, adjusting the sample position with respect to the X-ray beam using a pair of telescopes, and collecting diffraction data by raster scanning the sample with X-ray pulses. Named G-SITENNO, the other suite is an automated version of the original SITENNO suite, which was designed for processing diffraction data. These user-friendly software suites are now indispensable for collecting a large number of diffraction patterns and for processing the diffraction patterns immediately after collecting data within a limited beam time.

Anomalously enhanced hydration of aqueous electrolyte solution in hydrophobic carbon nanotubes to maintain stability.

PubMed

Ohba, Tomonori

2014-02-24

An understanding of the structure and behavior of electrolyte solutions in nanoenvironements is crucial not only for a wide variety of applications, but also for the development of physical, chemical, and biological processes. We demonstrate the structure and stability of electrolyte in carbon nanotubes using hybrid reverse Monte Carlo simulations of X-ray diffraction patterns. Hydrogen bonds between water are adequately formed in carbon nanotubes, although some hydrogen bonds are restricted by the interfaces of carbon nanotubes. The hydrogen bonding network of water in electrolyte in the carbon nanotubes is further weakened. On the other hand, formation of the ion hydration shell is significantly enhanced in the electrolyte in the carbon nanotubes in comparison to ion hydration in bulk electrolyte. The significant hydrogen bond and hydration shell formation are a result of gaining stability in the hydrophobic nanoenvironment. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembling of dihydroxypropyl 5,6-dihydrothymine derivatives

NASA Astrophysics Data System (ADS)

Cetina, Mario; Makarević, Janja; Nura-Lama, Afërdita

2010-09-01

( R, S)-1-(2',3'-Dibenzoyloxypropyl)-5,6-dihydrothymine ( 2) was synthesized from ( R, S)-1-(2',3'-dihydroxypropyl)-5,6-dihydrothymine and its structure has been analyzed by X-ray diffraction, NMR and FTIR spectroscopic methods. The molecular structure and supramolecular assembling of 2 is compared with the structure of its dimesyloxypropyl analogue ( 1). Compound 1 crystallizes as cocrystal of two diastereoisomers, while 2 crystallizes as a racemic mixture. Main hydrogen-bonded motif in both compounds is dimer formed by pair of N sbnd H···O( dbnd C) hydrogen bonds, which are further linked by C sbnd H···O hydrogen bonds. Phenyl rings of dibenzoyl-dihydropyrimidine moieties of 2 participate also in supramolecular aggregation via three C sbnd H···π interactions. Hydrogen bonding as driving force of 2 self-assembly was proving by the NMR and FTIR spectroscopy.

Synthesis of quenchable amorphous diamond

DOE PAGES

Zeng, Zhidan; Yang, Liuxiang; Zeng, Qiaoshi; ...

2017-08-22

Diamond owes its unique mechanical, thermal, optical, electrical, chemical, and biocompatible materials properties to its complete sp 3-carbon network bonding. Crystallinity is another major controlling factor for materials properties. Although other Group-14 elements silicon and germanium have complementary crystalline and amorphous forms consisting of purely sp 3 bonds, purely sp 3-bonded tetrahedral amorphous carbon has not yet been obtained. In this letter, we combine high pressure and in situ laser heating techniques to convert glassy carbon into “quenchable amorphous diamond”, and recover it to ambient conditions. Our X-ray diffraction, high-resolution transmission electron microscopy and electron energy-loss spectroscopy experiments on themore » recovered sample and computer simulations confirm its tetrahedral amorphous structure and complete sp 3 bonding. This transparent quenchable amorphous diamond has, to our knowledge, the highest density among amorphous carbon materials, and shows incompressibility comparable to crystalline diamond.« less

Synthesis of quenchable amorphous diamond

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zeng, Zhidan; Yang, Liuxiang; Zeng, Qiaoshi

Diamond owes its unique mechanical, thermal, optical, electrical, chemical, and biocompatible materials properties to its complete sp 3-carbon network bonding. Crystallinity is another major controlling factor for materials properties. Although other Group-14 elements silicon and germanium have complementary crystalline and amorphous forms consisting of purely sp 3 bonds, purely sp 3-bonded tetrahedral amorphous carbon has not yet been obtained. In this letter, we combine high pressure and in situ laser heating techniques to convert glassy carbon into “quenchable amorphous diamond”, and recover it to ambient conditions. Our X-ray diffraction, high-resolution transmission electron microscopy and electron energy-loss spectroscopy experiments on themore » recovered sample and computer simulations confirm its tetrahedral amorphous structure and complete sp 3 bonding. This transparent quenchable amorphous diamond has, to our knowledge, the highest density among amorphous carbon materials, and shows incompressibility comparable to crystalline diamond.« less

Supramolecular architecture based on [Fe(CN)6]3- metallotectons and melaminium synthons

NASA Astrophysics Data System (ADS)

Krichen, Firas; Walha, Siwar; Lhoste, Jérôme; Bulou, Alain; Kabadou, Ahlem; Goutenoire, François

2017-10-01

Assembly involving [Fe(CN)6]3- metallotectons as building units and melaminium organic cation has been envisioned in order to elaborate a hybrid supramolecular based on ionic H-bonds with formula {(H-mel)4[Fe(CN)6]Cl} (H-mel+: melaminium cation). The compound has been prepared by diffusion method and characterized by single-crystal X-ray diffraction, EDX analysis, and Raman-IR spectroscopies with assignment from ab initio calculations. The melaminium exhibit self cationic coupling with cyclic hydrogen bonds to give a one dimensional {[H-mel]+}∝ synthon. Therefore, these cationic ribbons are inter-linked via hydrogen bonds by the anionic tectons [Fe(CN)6]3- and chlorine anion resulting on a 3D network. Molecular hirshfeld surfaces revealed that the crystal structure has been supported mainly by Nsbnd H⋯N and Nsbnd H⋯Cl intermolecular Hydrogen bonds and by favoured C⋯C and C⋯N weak interactions.

Dynamical diffraction imaging (topography) with X-ray synchrotron radiation

NASA Technical Reports Server (NTRS)

Kuriyama, M.; Steiner, B. W.; Dobbyn, R. C.

1989-01-01

By contrast to electron microscopy, which yields information on the location of features in small regions of materials, X-ray diffraction imaging can portray minute deviations from perfect crystalline order over larger areas. Synchrotron radiation-based X-ray optics technology uses a highly parallel incident beam to eliminate ambiguities in the interpretation of image details; scattering phenomena previously unobserved are now readily detected. Synchrotron diffraction imaging renders high-resolution, real-time, in situ observations of materials under pertinent environmental conditions possible.

Development of Thin Films as Potential Structural Cathodes to Enable Multifunctional Energy-Storage Structural Composite Batteries for the U.S. Army’s Future Force

DTIC Science & Technology

2011-09-01

glancing angle X - ray diffraction (GAXRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), and electrochemical...Emission SEM FWHM full width at half maximum GAXRD glancing angle X - ray diffraction H3COCH2CH2OH 2-methoxyethanol LiMn2O4 lithium manganese oxide...were characterized by scanning electron microscopy (SEM), X - ray diffraction (XRD), and atomic force microscopy (AFM). In addition,

Simultaneous X-ray fluorescence and scanning X-ray diffraction microscopy at the Australian Synchrotron XFM beamline

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jones, Michael W. M.; Phillips, Nicholas W.; van Riessen, Grant A.

2016-08-11

Owing to its extreme sensitivity, quantitative mapping of elemental distributionsviaX-ray fluorescence microscopy (XFM) has become a key microanalytical technique. The recent realisation of scanning X-ray diffraction microscopy (SXDM) meanwhile provides an avenue for quantitative super-resolved ultra-structural visualization. The similarity of their experimental geometries indicates excellent prospects for simultaneous acquisition. Here, in both step- and fly-scanning modes, robust, simultaneous XFM-SXDM is demonstrated.

An Excel Spreadsheet for a One-Dimensional Fourier Map in X-ray Crystallography

ERIC Educational Resources Information Center

Clegg, William

2004-01-01

The teaching of crystal structure determination with single-crystal X-ray diffraction at undergraduate level faces numerous challenges. Single-crystal X-ray diffraction is used in a vast range of chemical research projects and forms the basis for a high proportion of structural results that are presented to high-school, undergraduate, and graduate…

Laser-induced Multi-energy Processing in Diamond Growth

DTIC Science & Technology

2012-05-01

microscopy (SEM) and energy dispersive X - ray (EDX) measurements, Drs. Yi Liu and Shah Valloppilly from Nebraska Center for Materials and Nanoscience...NCMN) at UNL for help on X - Ray diffraction (XRD) measurements, and Professor Steve W. Martin and Dr. Young Sik Kim from the Department of Material...spectroscopy and X - ray diffraction ................... 62 4.4 Conclusions

Synthesis and photoluminescence properties of silver(I) complexes based on N-benzoyl-L-glutamic acid and N-donor ligands with different flexibility

NASA Astrophysics Data System (ADS)

Yan, Ming-Jie; Feng, Qi; Song, Hui-Hua

2016-05-01

By changing the N-donor ancillary ligand, three novel silver (I) complexes {[Ag(HbzgluO) (4,4‧-bipy)]·H2O}n (1), {[Ag2(HbzgluO)2 (bpe)2]·2H2O}n (2) and {[Ag(HbzgluO)(bpp)]·2H2O}n (3) (H2bzgluO = N-benzoyl-L-glutamic acid, 4,4‧-bipy = 4,4ˊ-bipyridine, bpe = 1,2-di(4-pyridyl)ethane, bpp = 1,3-di(4-pyridyl)propane) were synthesized. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). In this study, the N-donor ligands are changed from rigidity (4,4‧-bipy), quasi-flexibility (bpe) to flexibility (bpp), the structures of complexes also change. Complex 1 features a 1D chain structure which is further linked together to construct a 2D supramolecular structure through hydrogen bonds. Complex 2 is a 1D double-chains configuration which eventually forms a 3D supramolecular network via hydrogen bonding interactions. Whereas, complex 3 exhibits a 2D pleated grid structure which is linked by hydrogen bonding interactions into a 3D supramolecular network. The present observations demonstrate that the modulation of coordination polymers with different structures can accomplish by changing the spacer length of N-donor ligands. In addition, the solid-state circular dichroism (CD) spectra indicated that compound 2 exhibited negative cotton effect which originated from the chiral ligands H2bzgluO and the solid-state fluorescence spectra of the three complexes demonstrated the auxiliary ligands have influence on the photoluminescence properties of the complexes.

Two-dimensional time-resolved X-ray diffraction study of liquid/solid fraction and solid particle size in Fe-C binary system with an electrostatic levitator furnace

NASA Astrophysics Data System (ADS)

Yonemura, M.; Okada, J.; Watanabe, Y.; Ishikawa, T.; Nanao, S.; Shobu, T.; Toyokawa, H.

2013-03-01

Liquid state provides functions such as matter transport or a reaction field and plays an important role in manufacturing processes such as refining, forging or welding. However, experimental procedures are significantly difficult for an observation of solidification process of iron and iron-based alloys in order to identify rapid transformations subjected to fast temperature evolution. Therefore, in order to study the solidification in iron and iron-based alloys, we considered a combination of high energy X-ray diffraction measurements and an electrostatic levitation method (ESL). In order to analyze the liquid/solid fraction, the solidification of melted spherical specimens was measured at a time resolution of 0.1 seconds during rapid cooling using the two-dimensional time-resolved X-ray diffraction. Furthermore, the observation of particle sizes and phase identification was performed on a trial basis using X-ray small angle scattering with X-ray diffraction.

Imaging single cells in a beam of live cyanobacteria with an X-ray laser.

PubMed

van der Schot, Gijs; Svenda, Martin; Maia, Filipe R N C; Hantke, Max; DePonte, Daniel P; Seibert, M Marvin; Aquila, Andrew; Schulz, Joachim; Kirian, Richard; Liang, Mengning; Stellato, Francesco; Iwan, Bianca; Andreasson, Jakob; Timneanu, Nicusor; Westphal, Daniel; Almeida, F Nunes; Odic, Dusko; Hasse, Dirk; Carlsson, Gunilla H; Larsson, Daniel S D; Barty, Anton; Martin, Andrew V; Schorb, Sebastian; Bostedt, Christoph; Bozek, John D; Rolles, Daniel; Rudenko, Artem; Epp, Sascha; Foucar, Lutz; Rudek, Benedikt; Hartmann, Robert; Kimmel, Nils; Holl, Peter; Englert, Lars; Duane Loh, Ne-Te; Chapman, Henry N; Andersson, Inger; Hajdu, Janos; Ekeberg, Tomas

2015-02-11

There exists a conspicuous gap of knowledge about the organization of life at mesoscopic levels. Ultra-fast coherent diffractive imaging with X-ray free-electron lasers can probe structures at the relevant length scales and may reach sub-nanometer resolution on micron-sized living cells. Here we show that we can introduce a beam of aerosolised cyanobacteria into the focus of the Linac Coherent Light Source and record diffraction patterns from individual living cells at very low noise levels and at high hit ratios. We obtain two-dimensional projection images directly from the diffraction patterns, and present the results as synthetic X-ray Nomarski images calculated from the complex-valued reconstructions. We further demonstrate that it is possible to record diffraction data to nanometer resolution on live cells with X-ray lasers. Extension to sub-nanometer resolution is within reach, although improvements in pulse parameters and X-ray area detectors will be necessary to unlock this potential.

Interplay between theory and experiment: computational organometallic and transition metal chemistry.

PubMed

Lin, Zhenyang

2010-05-18

Computational and theoretical chemistry provide fundamental insights into the structures, properties, and reactivities of molecules. As a result, theoretical calculations have become indispensable in various fields of chemical research and development. In this Account, we present our research in the area of computational transition metal chemistry, using examples to illustrate how theory impacts our understanding of experimental results and how close collaboration between theoreticians and experimental chemists can be mutually beneficial. We begin by examining the use of computational chemistry to elucidate the details of some unusual chemical bonds. We consider the three-center, two-electron bonding in titanocene sigma-borane complexes and the five-center, four-electron bonding in a rhodium-bismuth complex. The bonding in metallabenzene complexes is also examined. In each case, theoretical calculations provide particular insight into the electronic structure of the chemical bonds. We then give an example of how theoretical calculations aided the structural determination of a kappa(2)-N,N chelate ruthenium complex formed upon heating an intermediate benzonitrile-coordinated complex. An initial X-ray diffraction structure proposed on the basis of a reasonable mechanism appeared to fit well, with an apparently acceptable R value of 0.0478. But when DFT calculations were applied, the optimized geometry differed significantly from the experimental data. By combining experimental and theoretical outlooks, we posited a new structure. Remarkably, a re-refining of the X-ray diffraction data based on the new structure resulted in a slightly lower R value of 0.0453. We further examine the use of computational chemistry in providing new insight into C-H bond activation mechanisms and in understanding the reactivity properties of nucleophilic boryl ligands, addressing experimental difficulties with calculations and vice versa. Finally, we consider the impact of theoretical insights in three very specific experimental studies of chemical reactions, illustrating how theoretical results prompt further experimental studies: (i) diboration of aldehydes catalyzed by copper(I) boryl complexes, (ii) ruthenium-catalyzed C-H amination of arylazides, and (iii) zinc reduction of a vinylcarbyne complex. The concepts and examples presented here are intended for nonspecialists, particularly experimentalists. Together, they illustrate some of the achievements that are possible with a fruitful union of experiment and theory.

Anomalous magneto-elastic and charge doping effects in thallium-doped BaFe 2As 2

DOE PAGES

Sefat, Athena S.; Li, Li; Cao, Huibo B.; ...

2016-02-12

Within the BaFe 2As 2 crystal lattice, we partially substitute thallium for barium and report the effects of interlayer coupling in Ba 1-xTl xFe 2As 2 crystals. We demonstrate the unusual effects of magneto-elastic coupling and charge doping in this iron-arsenide material, whereby Néel temperature rises with small x, and then falls with additional x. Specifically, we find that Néel and structural transitions in BaFe 2As 2 (T N = T s = 133 K) increase for x = 0.05 (T N = 138 K, T s = 140 K) from magnetization, heat capacity, resistivity, and neutron diffraction measurements. Evidencemore » from single crystal X-ray diffraction and first principles calculations attributes the stronger magnetism in x = 0.05 to magneto-elastic coupling related to the shorter intraplanar Fe-Fe bond distance. With further thallium substitution, the transition temperatures decrease for x = 0.09 (T N = T s = 131 K), and this is due to charge doping. Lastly, we illustrate that small changes related to 3d transition-metal state can have profound effects on magnetism.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Chi; Boota, Muhammad; Urbankowski, Patrick

Restacking of two-dimensional (2D) flakes reduces the accessibility of electrolyte ions and is a problem in energy storage and other applications. Organic molecules can be used to prevent restacking and keep the interlayer space open. In this paper, we report on a combined theoretical and experimental investigation of the interaction between 2D titanium carbide (MXene), Ti 3C 2T x, and glycine. From first principle calculations, we presented the functionalization of glycine on the Ti 3C 2O 2 surface, evidenced by the shared electrons between Ti and N atoms. To experimentally validate our predictions, we synthesized flexible freestanding films of Timore » 3C 2T x/glycine hybrids. X-ray diffraction and X-ray photoelectron spectroscopy confirmed the increased interlayer spacing and possible Ti–N bonding, respectively, which agree with our theoretical predictions. Finally, the Ti 3C 2T x/glycine hybrid films exhibited an improved rate and cycling performances compared to pristine Ti 3C 2T x, possibly due to better charge percolation within expanded Ti 3C 2T x.« less

Effect of glycine functionalization of 2D titanium carbide (MXene) on charge storage

DOE PAGES

Chen, Chi; Boota, Muhammad; Urbankowski, Patrick; ...

2018-02-20

Restacking of two-dimensional (2D) flakes reduces the accessibility of electrolyte ions and is a problem in energy storage and other applications. Organic molecules can be used to prevent restacking and keep the interlayer space open. In this paper, we report on a combined theoretical and experimental investigation of the interaction between 2D titanium carbide (MXene), Ti 3C 2T x, and glycine. From first principle calculations, we presented the functionalization of glycine on the Ti 3C 2O 2 surface, evidenced by the shared electrons between Ti and N atoms. To experimentally validate our predictions, we synthesized flexible freestanding films of Timore » 3C 2T x/glycine hybrids. X-ray diffraction and X-ray photoelectron spectroscopy confirmed the increased interlayer spacing and possible Ti–N bonding, respectively, which agree with our theoretical predictions. Finally, the Ti 3C 2T x/glycine hybrid films exhibited an improved rate and cycling performances compared to pristine Ti 3C 2T x, possibly due to better charge percolation within expanded Ti 3C 2T x.« less

The 2:2 complex of pyridine betaine with squaric acid studied by X-ray diffraction, FTIR, NMR and DTG methods

NASA Astrophysics Data System (ADS)

Dega-Szafran, Z.; Dutkiewicz, G.; Kosturkiewicz, Z.

2012-12-01

The 2:2 ionic crystals of pyridine betaine (PyB) with squaric acid (H2SQ) belong to monoclinic space group C2/c. Supramolecular structure of the crystals investigated is formed by the loss of one proton from every two squaric acid molecules. Pyridine betaines form a homoconjugated cation, [(PyB)2H]+, through a short, symmetric COO⋯H⋯OOC hydrogen bond of 2.463(2) Å. The hydrogen squarate anions are linked into a homoconjugated anion, [(HSQ)2H]-, by a short symmetric, non-linear O⋯H⋯O hydrogen bond of 2.453(1) Å, with the H-atom located on the twofold axis. The bis(hydrogen squarate)hydrogen anions are linked into a centrosymmetric cyclic dimer by two identical asymmetric Osbnd H⋯O hydrogen bonds of 2.536(2) Å. The (PyB)2H cation and cyclic dimer of hydrogen squarate anions are placed around two different systems of inversion centers in the unit cell. The FTIR spectrum is consistent with the X-ray results. The 13C chemical shift of the Cdbnd O atom confirms the presence of the hydrogen squarate anion in the complex studied. The complex decomposed in three thermal stages.

Exploring contribution of intermolecular interactions in supramolecular layered assembly of naphthyridine co-crystals: Insights from Hirshfeld surface analysis of their crystalline states

NASA Astrophysics Data System (ADS)

Seth, Saikat Kumar; Das, Nirmal Kumar; Aich, Krishnendu; Sen, Debabrata; Fun, Hoong-Kun; Goswami, Shyamaprasad

2013-09-01

Co-crystals of 1a and 1b have been prepared by slow evaporation of the solutions of mixtures of 2,7-dimethyl-1,8-naphthyridine (1), urea (a) and thiourea (b). The structures of the complexes are determined by the single crystal X-ray diffraction and a detailed investigation of the crystal packing and classification of intermolecular interactions is presented by means of Hirshfeld surface analysis which is of considerable current interest in crystal engineering. The X-ray study reveals that the co-crystal formers are envisioned to produce N-H⋯N hydrogen bond as well as N-H⋯O/N-H⋯S pair-wise hydrogen bonds and also the weaker aromatic π⋯π interactions which cooperatively take part in the crystal packing. The recurring feature of the self-assembly in the compounds is the appearance of the molecular ribbon through multiple hydrogen bonding which are further stacked into molecular layers by π⋯π stacking interactions. Hirshfeld surface analysis for visually analyzing intermolecular interactions in crystal structures employing molecular surface contours and 2D Fingerprint plots have been used to examine molecular shapes. Crystal structure analysis supported with the Hirshfeld surface and fingerprint plots enabled the identification of the significant intermolecular interactions.

Comparison of Erosion Behavior and Particle Contamination in Mass-Production CF4/O2 Plasma Chambers Using Y2O3 and YF3 Protective Coatings

PubMed Central

Lin, Tzu-Ken; Wang, Wei-Kai; Huang, Shih-Yung; Tasi, Chi-Tsung

2017-01-01

Yttrium fluoride (YF3) and yttrium oxide (Y2O3) protective coatings prepared using an atmospheric plasma spraying technique were used to investigate the relationship between surface erosion behaviors and their nanoparticle generation under high-density plasma (1012–1013 cm−3) etching. As examined by transmission electron microscopy, the Y2O3 and YF3 coatings become oxyfluorinated after exposure to the plasma, wherein the yttrium oxyfluoride film formation was observed on the surface with a thickness of 5.2 and 6.8 nm, respectively. The difference in the oxyfluorination of Y2O3 and YF3 coatings could be attributed to Y–F and Y–O bonding energies. X-ray photoelectron spectroscopy analyses revealed that a strongly fluorinated bonding (Y–F bond) was obtained on the etched surface of the YF3 coating. Scanning electron microscopy and energy dispersive X-ray diffraction analysis revealed that the nanoparticles on the 12-inch wafer are composed of etchant gases and Y2O3. These results indicate that the YF3 coating is a more erosion-resistant material, resulting in fewer contamination particles compared with the Y2O3 coating. PMID:28708079

Luminescent properties under X-ray excitation of Ba(1-x)PbxWO4 disordered solid solution

NASA Astrophysics Data System (ADS)

Bakiz, B.; Hallaoui, A.; Taoufyq, A.; Benlhachemi, A.; Guinneton, F.; Villain, S.; Ezahri, M.; Valmalette, J.-C.; Arab, M.; Gavarri, J.-R.

2018-02-01

A series of polycrystalline barium-lead tungstate Ba1-xPbxWO4 with 0 ≤ x ≤ 1 was synthesized using a classical solid-state method with thermal treatment at 1000 °C. These materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Raman (FT-Raman) spectroscopy. X-ray diffraction profile analyses were performed using Rietveld method. These materials crystallized in the scheelite tetragonal structure and behaved as quasi ideal solid solution. Raman spectroscopy confirmed the formation of the solid solution. Structural distortions were evidenced in X-ray diffraction profiles and in vibration Raman spectra. The scanning electron microscopy experiments showed large and rounded irregular grains. Luminescence experiments were performed under X-ray excitation. The luminescence emission profiles have been interpreted in terms of four Gaussian components, with a major contribution of blue emission. The integrated intensity of luminescence reached a maximum value in the composition range x = 0.3-0.6, in relation with distortions of crystal lattice.

Amorphous Phase Characterization Through X-Ray Diffraction Profile Modeling: Implications for Amorphous Phases in Gale Crater Rocks and Soils

NASA Technical Reports Server (NTRS)

Achilles, C. N.; Downs, G. W.; Downs, R. T.; Morris, R. V.; Rampe, E. B.; Ming, D. W.; Chipera, S. J.; Blake, D. F.; Vaniman, D. T.; Bristow, T. F.;

Cu(II) coordination polymers constructed by tetrafluoroterephthalic acid and varied imidazole-containing ligands: Syntheses, structures and properties

NASA Astrophysics Data System (ADS)

Liu, Kang; Sun, Yayong; Deng, Liming; Cao, Fan; Han, Jishu; Wang, Lei

2018-02-01

Six new copper(II) coordination polymers combining 2,3,5,6-tetrafluoroterephthalatic acid (H2tfBDC) and diverse imidazole-containing ligands, {[Cu(tfBDC)(1,2-bix)2]·2(H2O)}n (1), {Cu(tfBDC)(Im)2}n (2), {[Cu(1,4-bmimb)2(H2O)]·(tfBDC)·2(H2O)}n (3), {Cu(1,4-bimb)2(H2O)2·(tfBDC)}n (4), {[Cu(1,3-bix)2(H2O)2]·(tfBDC)·6(H2O)}n (5) and {[Cu(1,4-bix)2(H2O)2]·(tfBDC)·(1,4-bix)·4(H2O)}n (6) (1,2-bix = 1,2-bis(imidazole-1-ylmethyl)-benzene, Im = imidazole, 1,4-bmimb = 1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene, 1,4-bimb = 1,4-bis(imidazol-1-yl)-butane, 1,3-bix = 1,3-bis(imidazole-1-ylmethyl)-benzene, 1,4-bix = 1,4-bis(imidazole-1-ylmethyl)-benzene), have been obtained and structurally verified by single-crystal X-ray diffraction analyses and further characterized by powder X-ray diffraction (PXRD), elemental analyses and infrared spectroscopy (IR). Single crystal X-ray diffraction analysis revealed that 1 is 2D 4-connected sql topology (point symbol: {44·62}) based on a single metal ion node. Compound 2 is characterized as an infinite 1D chain structure, which is further extended into a 2D layer through N-H···O hydrogen bonds and then a 3D supramolecular architecture via π···π stacking interactions. Note that 2 was prepared through an in situ ligand reaction in which N,N'-carbonyldiimidazole (cdi) broke up into imidazole ligand. Compound 3 possesses a 3D 4-fold interpenetrated architecture with 4-connected dia topology (Schläfli symbol: {66}) in which tfBDC2- is stabilized in the channel by hydrogen bonds. Compounds 4-6 are all linear 1D coordination polymers. In 4, the free tfBDC2- ligand acts as a μ4-bridge to link four coordinated water molecules from the chain to construct a 2D structure via hydrogen bonds. While in 5 and 6, the uncoordinated tfBDC2- ligands and multimeric water clusters is responsible for the conversion of these 1D coordination polymers into 3D supramolecular assemblies through O-H⋯O hydrogen bonding interactions. Moreover, the UV-vis spectra and thermal stability of 1-6 are discussed in detail.

Molecular simulations and density functional theory calculations of bromine in clathrate hydrate phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dureckova, Hana, E-mail: houci059@uottawa.ca; Woo, Tom K., E-mail: tom.woo@uottawa.ca; Alavi, Saman, E-mail: saman.alavi@nrc-cnrc.gc.ca

Bromine forms a tetragonal clathrate hydrate structure (TS-I) very rarely observed in clathrate hydrates of other guest substances. The detailed structure, energetics, and dynamics of Br{sub 2} and Cl{sub 2} in TS-I and cubic structure I (CS-I) clathrate hydrates are studied in this work using molecular dynamics and quantum chemical calculations. X-ray diffraction studies show that the halogen-water–oxygen distances in the cages of these structures are shorter than the sum of the van der Waals radii of halogen and oxygen atoms. This suggests that the stabilizing effects of halogen bonding or other non-covalent interactions (NCIs) may contribute to the formationmore » of the unique tetragonal bromine hydrate structure. We performed molecular dynamics simulations of Br{sub 2} and Cl{sub 2} clathrate hydrates using our previously developed five-site charge models for the dihalogen molecules [Dureckova et al. Can. J. Chem. 93, 864 (2015)] which reproduce the computed electrostatic potentials of the dihalogens and account for the electropositive σ-hole of the halogen bond donor (the dihalogen). Analysis of the radial distribution functions, enthalpies of encapsulation, velocity and orientation autocorrelation functions, and polar angle distributions are carried out for Br{sub 2} and Cl{sub 2} guests in various cages to contrast the properties of these guests in the TS-I and CS-I phases. Quantum chemical partial geometry optimizations of Br{sub 2} and Cl{sub 2} guests in the hydrate cages using the M06-2X functional give short halogen-water distances compatible with values observed in X-ray diffraction experiments. NCI plots of guest-cage structures are generated to qualitatively show the relative strength of the non-bonding interactions between dihalogens and water molecules. The differences between behaviors of Br{sub 2} and Cl{sub 2} guests in the hydrate cages may explain why bromine forms the unique TS-I phase.« less

X-ray Diffraction, Big and Small

NASA Image and Video Library

2012-10-30

A conventional X-ray diffraction instrument left is the size of a large refrigerator, in contrast to the compact size of the Chemistry and Mineralogy CheMin instrument on NASA Curiosity rover top right.

Coherent diffraction of single Rice Dwarf virus particles using hard X-rays at the Linac Coherent Light Source

PubMed Central

Munke, Anna; Andreasson, Jakob; Aquila, Andrew; Awel, Salah; Ayyer, Kartik; Barty, Anton; Bean, Richard J.; Berntsen, Peter; Bielecki, Johan; Boutet, Sébastien; Bucher, Maximilian; Chapman, Henry N.; Daurer, Benedikt J.; DeMirci, Hasan; Elser, Veit; Fromme, Petra; Hajdu, Janos; Hantke, Max F.; Higashiura, Akifumi; Hogue, Brenda G.; Hosseinizadeh, Ahmad; Kim, Yoonhee; Kirian, Richard A.; Reddy, Hemanth K.N.; Lan, Ti-Yen; Larsson, Daniel S.D.; Liu, Haiguang; Loh, N. Duane; Maia, Filipe R.N.C.; Mancuso, Adrian P.; Mühlig, Kerstin; Nakagawa, Atsushi; Nam, Daewoong; Nelson, Garrett; Nettelblad, Carl; Okamoto, Kenta; Ourmazd, Abbas; Rose, Max; van der Schot, Gijs; Schwander, Peter; Seibert, M. Marvin; Sellberg, Jonas A.; Sierra, Raymond G.; Song, Changyong; Svenda, Martin; Timneanu, Nicusor; Vartanyants, Ivan A.; Westphal, Daniel; Wiedorn, Max O.; Williams, Garth J.; Xavier, Paulraj Lourdu; Yoon, Chun Hong; Zook, James

2016-01-01

Single particle diffractive imaging data from Rice Dwarf Virus (RDV) were recorded using the Coherent X-ray Imaging (CXI) instrument at the Linac Coherent Light Source (LCLS). RDV was chosen as it is a well-characterized model system, useful for proof-of-principle experiments, system optimization and algorithm development. RDV, an icosahedral virus of about 70 nm in diameter, was aerosolized and injected into the approximately 0.1 μm diameter focused hard X-ray beam at the CXI instrument of LCLS. Diffraction patterns from RDV with signal to 5.9 Ångström were recorded. The diffraction data are available through the Coherent X-ray Imaging Data Bank (CXIDB) as a resource for algorithm development, the contents of which are described here. PMID:27478984

Signal-to-noise and radiation exposure considerations in conventional and diffraction x-ray microscopy

DOE PAGES

Huang, Xiaojing; Miao, Huijie; Steinbrener, Jan; ...

2009-01-01

Using a signal-to-noise ratio estimation based on correlations between multiple simulated images, we compare the dose efficiency of two soft x-ray imaging systems: incoherent brightfield imaging using zone plate optics in a transmission x-ray microscope (TXM), and x-ray diffraction microscopy (XDM) where an image is reconstructed from the far-field coherent diffraction pattern. In XDM one must computationally phase weak diffraction signals; in TXM one suffers signal losses due to the finite numerical aperture and efficiency of the optics. In simulations with objects representing isolated cells such as yeast, we find that XDM has the potential for delivering equivalent resolution imagesmore » using fewer photons. As a result, this can be an important advantage for studying radiation-sensitive biological and soft matter specimens.« less

Utilizing broadband X-rays in a Bragg coherent X-ray diffraction imaging experiment

DOE PAGES

Cha, Wonsuk; Liu, Wenjun; Harder, Ross; ...

2016-07-26

A method is presented to simplify Bragg coherent X-ray diffraction imaging studies of complex heterogeneous crystalline materials with a two-stage screening/imaging process that utilizes polychromatic and monochromatic coherent X-rays and is compatible with in situ sample environments. Coherent white-beam diffraction is used to identify an individual crystal particle or grain that displays desired properties within a larger population. A three-dimensional reciprocal-space map suitable for diffraction imaging is then measured for the Bragg peak of interest using a monochromatic beam energy scan that requires no sample motion, thus simplifyingin situchamber design. This approach was demonstrated with Au nanoparticles and will enable,more » for example, individual grains in a polycrystalline material of specific orientation to be selected, then imaged in three dimensions while under load.« less

Coherent diffraction of single Rice Dwarf virus particles using hard X-rays at the Linac Coherent Light Source

DOE PAGES

Munke, Anna; Andreasson, Jakob; Aquila, Andrew; ...

2016-08-01

Single particle diffractive imaging data from Rice Dwarf Virus (RDV) were recorded using the Coherent X-ray Imaging (CXI) instrument at the Linac Coherent Light Source (LCLS). RDV was chosen as it is a well-characterized model system, useful for proof-of-principle experiments, system optimization and algorithm development. RDV, an icosahedral virus of about 70 nm in diameter, was aerosolized and injected into the approximately 0.1 μm diameter focused hard X-ray beam at the CXI instrument of LCLS. Diffraction patterns from RDV with signal to 5.9 Ångström were recorded. Here, the diffraction data are available through the Coherent X-ray Imaging Data Bank (CXIDB)more » as a resource for algorithm development, the contents of which are described here.« less

Influence of neutron irradiation on the microstructure of nuclear graphite: An X-ray diffraction study

NASA Astrophysics Data System (ADS)

Zhou, Z.; Bouwman, W. G.; Schut, H.; van Staveren, T. O.; Heijna, M. C. R.; Pappas, C.

2017-04-01

Neutron irradiation effects on the microstructure of nuclear graphite have been investigated by X-ray diffraction on virgin and low doses (∼ 1.3 and ∼ 2.2 dpa), high temperature (750° C) irradiated samples. The diffraction patterns were interpreted using a model, which takes into account the turbostratic disorder. Besides the lattice constants, the model introduces two distinct coherent lengths in the c-axis and the basal plane, that characterise the volumes from which X-rays are scattered coherently. The methodology used in this work allows to quantify the effect of irradiation damage on the microstructure of nuclear graphite seen by X-ray diffraction. The results show that the changes of the deduced structural parameters are in agreement with previous observations from electron microscopy, but not directly related to macroscopic changes.

Utilizing broadband X-rays in a Bragg coherent X-ray diffraction imaging experiment.

PubMed

Cha, Wonsuk; Liu, Wenjun; Harder, Ross; Xu, Ruqing; Fuoss, Paul H; Hruszkewycz, Stephan O

2016-09-01

A method is presented to simplify Bragg coherent X-ray diffraction imaging studies of complex heterogeneous crystalline materials with a two-stage screening/imaging process that utilizes polychromatic and monochromatic coherent X-rays and is compatible with in situ sample environments. Coherent white-beam diffraction is used to identify an individual crystal particle or grain that displays desired properties within a larger population. A three-dimensional reciprocal-space map suitable for diffraction imaging is then measured for the Bragg peak of interest using a monochromatic beam energy scan that requires no sample motion, thus simplifying in situ chamber design. This approach was demonstrated with Au nanoparticles and will enable, for example, individual grains in a polycrystalline material of specific orientation to be selected, then imaged in three dimensions while under load.

Time-spliced X-ray diffraction imaging of magnetism dynamics in a NdNiO3 thin film

NASA Astrophysics Data System (ADS)

Beyerlein, Kenneth R.

2018-03-01

Diffraction imaging of nonequilibrium dynamics at atomic resolution is becoming possible with X-ray free-electron lasers. However, there are unresolved problems with applying this method to objects that are confined in only one dimension. Here I show that reliable one-dimensional coherent diffraction imaging is possible by splicing together images recovered from different time delays in an optical pump X-ray probe experiment. The time and space evolution of antiferromagnetic order in a vibrationally excited complex oxide heterostructure is recovered from time-resolved measurements of a resonant soft X-ray diffraction peak. Midinfrared excitation of the substrate is shown to lead to a demagnetization front that propagates at a velocity exceeding the speed of sound, a critical observation for the understanding of driven phase transitions in complex condensed matter.

Coherent diffraction of single Rice Dwarf virus particles using hard X-rays at the Linac Coherent Light Source.

PubMed

Munke, Anna; Andreasson, Jakob; Aquila, Andrew; Awel, Salah; Ayyer, Kartik; Barty, Anton; Bean, Richard J; Berntsen, Peter; Bielecki, Johan; Boutet, Sébastien; Bucher, Maximilian; Chapman, Henry N; Daurer, Benedikt J; DeMirci, Hasan; Elser, Veit; Fromme, Petra; Hajdu, Janos; Hantke, Max F; Higashiura, Akifumi; Hogue, Brenda G; Hosseinizadeh, Ahmad; Kim, Yoonhee; Kirian, Richard A; Reddy, Hemanth K N; Lan, Ti-Yen; Larsson, Daniel S D; Liu, Haiguang; Loh, N Duane; Maia, Filipe R N C; Mancuso, Adrian P; Mühlig, Kerstin; Nakagawa, Atsushi; Nam, Daewoong; Nelson, Garrett; Nettelblad, Carl; Okamoto, Kenta; Ourmazd, Abbas; Rose, Max; van der Schot, Gijs; Schwander, Peter; Seibert, M Marvin; Sellberg, Jonas A; Sierra, Raymond G; Song, Changyong; Svenda, Martin; Timneanu, Nicusor; Vartanyants, Ivan A; Westphal, Daniel; Wiedorn, Max O; Williams, Garth J; Xavier, Paulraj Lourdu; Yoon, Chun Hong; Zook, James

2016-08-01

Single particle diffractive imaging data from Rice Dwarf Virus (RDV) were recorded using the Coherent X-ray Imaging (CXI) instrument at the Linac Coherent Light Source (LCLS). RDV was chosen as it is a well-characterized model system, useful for proof-of-principle experiments, system optimization and algorithm development. RDV, an icosahedral virus of about 70 nm in diameter, was aerosolized and injected into the approximately 0.1 μm diameter focused hard X-ray beam at the CXI instrument of LCLS. Diffraction patterns from RDV with signal to 5.9 Ångström were recorded. The diffraction data are available through the Coherent X-ray Imaging Data Bank (CXIDB) as a resource for algorithm development, the contents of which are described here.

Time-spliced X-ray diffraction imaging of magnetism dynamics in a NdNiO3 thin film.

PubMed

Beyerlein, Kenneth R

2018-02-27

Diffraction imaging of nonequilibrium dynamics at atomic resolution is becoming possible with X-ray free-electron lasers. However, there are unresolved problems with applying this method to objects that are confined in only one dimension. Here I show that reliable one-dimensional coherent diffraction imaging is possible by splicing together images recovered from different time delays in an optical pump X-ray probe experiment. The time and space evolution of antiferromagnetic order in a vibrationally excited complex oxide heterostructure is recovered from time-resolved measurements of a resonant soft X-ray diffraction peak. Midinfrared excitation of the substrate is shown to lead to a demagnetization front that propagates at a velocity exceeding the speed of sound, a critical observation for the understanding of driven phase transitions in complex condensed matter.

Preliminary small-angle X-ray scattering and X-ray diffraction studies of the BTB domain of lola protein from Drosophila melanogaster

NASA Astrophysics Data System (ADS)

Boyko, K. M.; Nikolaeva, A. Yu.; Kachalova, G. S.; Bonchuk, A. N.; Dorovatovskii, P. V.; Popov, V. O.

2017-11-01

The Drosophila genome has several dozens of transcription factors (TTK group) containing BTB domains assembled into octamers. The LOLA protein belongs to this family. The purification, crystallization, and preliminary X-ray diffraction and small-angle X-ray scattering (SAXS) studies of the BTB domain of this protein are reported. The crystallization conditions were found by the vapor-diffusion technique. A very low diffraction resolution (8.7 Å resolution) of the crystals was insufficient for the determination of the threedimensional structure of the BTB domain. The SAXS study demonstrated that the BTB domain of the LOLA protein exists as an octamer in solution.

Cryogenic x-ray diffraction microscopy utilizing high-pressure cryopreservation

NASA Astrophysics Data System (ADS)

Lima, Enju; Chushkin, Yuriy; van der Linden, Peter; Kim, Chae Un; Zontone, Federico; Carpentier, Philippe; Gruner, Sol M.; Pernot, Petra

2014-10-01

We present cryo x-ray diffraction microscopy of high-pressure-cryofixed bacteria and report high-convergence imaging with multiple image reconstructions. Hydrated D. radiodurans cells were cryofixed at 200 MPa pressure into ˜10-μm-thick water layers and their unstained, hydrated cellular environments were imaged by phasing diffraction patterns, reaching sub-30-nm resolutions with hard x-rays. Comparisons were made with conventional ambient-pressure-cryofixed samples, with respect to both coherent small-angle x-ray scattering and the image reconstruction. The results show a correlation between the level of background ice signal and phasing convergence, suggesting that phasing difficulties with frozen-hydrated specimens may be caused by high-background ice scattering.

Synchrotron X-ray powder diffraction data of LASSBio-1515: A new N-acylhydrazone derivative compound

NASA Astrophysics Data System (ADS)

Costa, F. N.; Braz, D.; Ferreira, F. F.; da Silva, T. F.; Barreiro, E. J.; Lima, L. M.; Colaço, M. V.; Kuplich, L.; Barroso, R. C.

2014-02-01

In this work, synchrotron X-ray powder diffraction data allowed for a successful indexing of LASSBio-1515 compound, candidate to analgesic and anti-inflammatory activity. X-ray powder diffraction data collected in transmission and high-throughput geometries were used to analyze this compound. The X-ray wavelength of the synchrotron radiation used in this study was determined to be λ=1.55054 Å. LASSBio-1515 was found to be monoclinic with space group P21/c and unit cell parameters a=11.26255(16) Å, b=12.59785(16) Å, c=8.8540(1) Å, β=90.5972(7)° and V=1256.17(3) Å3.

High-speed classification of coherent X-ray diffraction patterns on the K computer for high-resolution single biomolecule imaging.

PubMed

Tokuhisa, Atsushi; Arai, Junya; Joti, Yasumasa; Ohno, Yoshiyuki; Kameyama, Toyohisa; Yamamoto, Keiji; Hatanaka, Masayuki; Gerofi, Balazs; Shimada, Akio; Kurokawa, Motoyoshi; Shoji, Fumiyoshi; Okada, Kensuke; Sugimoto, Takashi; Yamaga, Mitsuhiro; Tanaka, Ryotaro; Yokokawa, Mitsuo; Hori, Atsushi; Ishikawa, Yutaka; Hatsui, Takaki; Go, Nobuhiro

2013-11-01

Single-particle coherent X-ray diffraction imaging using an X-ray free-electron laser has the potential to reveal the three-dimensional structure of a biological supra-molecule at sub-nanometer resolution. In order to realise this method, it is necessary to analyze as many as 1 × 10(6) noisy X-ray diffraction patterns, each for an unknown random target orientation. To cope with the severe quantum noise, patterns need to be classified according to their similarities and average similar patterns to improve the signal-to-noise ratio. A high-speed scalable scheme has been developed to carry out classification on the K computer, a 10PFLOPS supercomputer at RIKEN Advanced Institute for Computational Science. It is designed to work on the real-time basis with the experimental diffraction pattern collection at the X-ray free-electron laser facility SACLA so that the result of classification can be feedback for optimizing experimental parameters during the experiment. The present status of our effort developing the system and also a result of application to a set of simulated diffraction patterns is reported. About 1 × 10(6) diffraction patterns were successfully classificatied by running 255 separate 1 h jobs in 385-node mode.

High-speed classification of coherent X-ray diffraction patterns on the K computer for high-resolution single biomolecule imaging

PubMed Central

Tokuhisa, Atsushi; Arai, Junya; Joti, Yasumasa; Ohno, Yoshiyuki; Kameyama, Toyohisa; Yamamoto, Keiji; Hatanaka, Masayuki; Gerofi, Balazs; Shimada, Akio; Kurokawa, Motoyoshi; Shoji, Fumiyoshi; Okada, Kensuke; Sugimoto, Takashi; Yamaga, Mitsuhiro; Tanaka, Ryotaro; Yokokawa, Mitsuo; Hori, Atsushi; Ishikawa, Yutaka; Hatsui, Takaki; Go, Nobuhiro

2013-01-01

Single-particle coherent X-ray diffraction imaging using an X-ray free-electron laser has the potential to reveal the three-dimensional structure of a biological supra-molecule at sub-nanometer resolution. In order to realise this method, it is necessary to analyze as many as 1 × 106 noisy X-ray diffraction patterns, each for an unknown random target orientation. To cope with the severe quantum noise, patterns need to be classified according to their similarities and average similar patterns to improve the signal-to-noise ratio. A high-speed scalable scheme has been developed to carry out classification on the K computer, a 10PFLOPS supercomputer at RIKEN Advanced Institute for Computational Science. It is designed to work on the real-time basis with the experimental diffraction pattern collection at the X-ray free-electron laser facility SACLA so that the result of classification can be feedback for optimizing experimental parameters during the experiment. The present status of our effort developing the system and also a result of application to a set of simulated diffraction patterns is reported. About 1 × 106 diffraction patterns were successfully classificatied by running 255 separate 1 h jobs in 385-node mode. PMID:24121336

Elucidating the Wavelength Dependence of Phonon Scattering in Nanoparticle-Matrix Composites using Phonon Spectroscopy

DTIC Science & Technology

2016-07-11

composites with x - ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Rutherford backscattering spectroscopy...RBS), particle-induced x - ray emission (PIXE), and energy dispersive x - ray spectroscopy (EDX). This work complements earlier works on CdSe...sample shows only In2Se3 and CdIn2Se4 XRD peaks (Figure 1.4e), it is stoichiometrically   Figure 1.4. X - ray diffraction patterns of (a) γ-In2Se3

Applications of High Throughput (Combinatorial) Methodologies to Electronic, Magnetic, Optical, and Energy-Related Materials

DTIC Science & Technology

2013-06-17

of the films without having to fabricate capacitors. In addition, the use of X - ray diffraction (XRD) analysis enabled Chikyow et al.40 to identify an...effects of Al doping and annealing on the thermal stabil- ity of the Y2O3/Si gate stack were studied by X - ray photoemission spectroscopy (XPS) and X - ray ...the major diffraction features in the phase distribution. For a given structural phase, the X - ray peak intensity allows one to track the compositional

Aplanatic and quasi-aplanatic diffraction gratings

DOEpatents

Hettrick, M.C.

1987-09-14

A reflection diffraction grating having a series of transverse minute grooves of progressively varying spacing along a concave surface enables use of such gratings for x-ray or longer wavelength imaging of objects. The variable groove spacing establishes aplanatism or substantially uniform magnetification across the optical aperture. The grating may be sued, for example, in x-ray microscopes or telescopes of the imaging type and in x-ray microprobed. Increased spatial resolution and field of view may be realized in x-ray imaging. 5 figs.

An instrument for in situ coherent x-ray studies of metal-organic vapor phase epitaxy of III-nitrides

DOE PAGES

Ju, Guangxu; Highland, Matthew J.; Yanguas-Gil, Angel; ...

2017-03-21

Here, we describe an instrument that exploits the ongoing revolution in synchrotron sources, optics, and detectors to enable in situ studies of metal-organic vapor phase epitaxy (MOVPE) growth of III-nitride materials using coherent x-ray methods. The system includes high-resolution positioning of the sample and detector including full rotations, an x-ray transparent chamber wall for incident and diffracted beam access over a wide angular range, and minimal thermal sample motion, giving the sub-micron positional stability and reproducibility needed for coherent x-ray studies. The instrument enables surface x-ray photon correlation spectroscopy, microbeam diffraction, and coherent diffraction imaging of atomic-scale surface and filmmore » structure and dynamics during growth, to provide fundamental understanding of MOVPE processes.« less

Towards shot-noise limited diffraction experiments with table-top femtosecond hard x-ray sources.

PubMed

Holtz, Marcel; Hauf, Christoph; Weisshaupt, Jannick; Salvador, Antonio-Andres Hernandez; Woerner, Michael; Elsaesser, Thomas

2017-09-01

Table-top laser-driven hard x-ray sources with kilohertz repetition rates are an attractive alternative to large-scale accelerator-based systems and have found widespread applications in x-ray studies of ultrafast structural dynamics. Hard x-ray pulses of 100 fs duration have been generated at the Cu K α wavelength with a photon flux of up to 10 9 photons per pulse into the full solid angle, perfectly synchronized to the sub-100-fs optical pulses from the driving laser system. Based on spontaneous x-ray emission, such sources display a particular noise behavior which impacts the sensitivity of x-ray diffraction experiments. We present a detailed analysis of the photon statistics and temporal fluctuations of the x-ray flux, together with experimental strategies to optimize the sensitivity of optical pump/x-ray probe experiments. We demonstrate measurements close to the shot-noise limit of the x-ray source.

Towards shot-noise limited diffraction experiments with table-top femtosecond hard x-ray sources

PubMed Central

Holtz, Marcel; Hauf, Christoph; Weisshaupt, Jannick; Salvador, Antonio-Andres Hernandez; Woerner, Michael; Elsaesser, Thomas

2017-01-01

Table-top laser-driven hard x-ray sources with kilohertz repetition rates are an attractive alternative to large-scale accelerator-based systems and have found widespread applications in x-ray studies of ultrafast structural dynamics. Hard x-ray pulses of 100 fs duration have been generated at the Cu Kα wavelength with a photon flux of up to 109 photons per pulse into the full solid angle, perfectly synchronized to the sub-100-fs optical pulses from the driving laser system. Based on spontaneous x-ray emission, such sources display a particular noise behavior which impacts the sensitivity of x-ray diffraction experiments. We present a detailed analysis of the photon statistics and temporal fluctuations of the x-ray flux, together with experimental strategies to optimize the sensitivity of optical pump/x-ray probe experiments. We demonstrate measurements close to the shot-noise limit of the x-ray source. PMID:28795079

Aligning, Bonding, and Testing Mirrors for Lightweight X-ray Telescopes

NASA Technical Reports Server (NTRS)

Chan, Kai-Wing; Zhang, William W.; Saha, Timo T.; McClelland, Ryan S.; Biskach, Michael P.; Niemeyer, Jason; Schofield, Mark J.; Mazzarella, James R.; Kolos, Linette D.; Hong, Melinda M.;

X-ray shearing interferometer

DOEpatents

Koch, Jeffrey A [Livermore, CA

2003-07-08

An x-ray interferometer for analyzing high density plasmas and optically opaque materials includes a point-like x-ray source for providing a broadband x-ray source. The x-rays are directed through a target material and then are reflected by a high-quality ellipsoidally-bent imaging crystal to a diffraction grating disposed at 1.times. magnification. A spherically-bent imaging crystal is employed when the x-rays that are incident on the crystal surface are normal to that surface. The diffraction grating produces multiple beams which interfere with one another to produce an interference pattern which contains information about the target. A detector is disposed at the position of the image of the target produced by the interfering beams.

Raman spectroscopy and x-ray diffraction of sp 3 CaC O 3 at lower mantle pressures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lobanov, Sergey S.; Dong, Xiao; Martirosyan, Naira S.

The exceptional ability of carbon to form sp 2 and sp 3 bonding states leads to a great structural and chemical diversity of carbon-bearing phases at nonambient conditions. Here we use laser-heated diamond-anvil cells combined with synchrotron x-ray diffraction, Raman spectroscopy, and first-principles calculations to explore phase transitions in CaC O 3 at P > 40 GPa . We find that postaragonite CaC O 3 transforms to the previously predicted P 2 1 / c CaC O 3 with sp 3 -hybridized carbon at 105 GPa ( ~ 30 GPa higher than the theoretically predicted crossovermore » pressure). The lowest-enthalpy transition path to P2 1 / c CaC O 3 includes reoccurring sp 2 and sp 3 CaC O 3 intermediate phases and transition states, as revealed by our variable-cell nudged-elastic-band simulation. Raman spectra of P 2 1 / c CaC O 3 show an intense band at 1025 c m -1 , which we assign to the symmetric C-O stretching vibration based on empirical and first-principles calculations. This Raman band has a frequency that is ~ 20 % low-ymmetric C-O stretching in sp 2 CaC O 3 due to the C-O bond length increase across the sp 2 ~ sp 3 transition and can be used as a fingerprint of tetrahedrally coordinated carbon in other carbonates.« less

Synthesis, spectroscopic and theoretical studies of ethyl (2E)-3-amino-2-({[(4-benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)carbonyl]amino}carbonothioyl)but-2-enoate butanol solvate

NASA Astrophysics Data System (ADS)

Koca, İrfan; Sert, Yusuf; Gümüş, Mehmet; Kani, İbrahim; Çırak, Çağrı

2014-01-01

We have synthesized ethyl (2E)-3-amino-2-({[(4-benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)carbonyl]amino}carbonothioyl)but-2-enoate (2) by the reaction of 4-benzoyl-1,5-diphenyl-1H-pyrazole-3-carbonyl chloride (1), ammonium thiocyanate and ethyl 3-aminobut-2-enoate and then characterized by elemental analyses, IR, Raman, 1H NMR, 13C NMR and X-ray diffraction methods. The experimental and theoretical vibrational spectra of 2 were investigated. The experimental FT-IR (4000-400 cm-1) and Laser-Raman spectra (4000-100 cm-1) of the molecule in the solid phase were recorded. Theoretical vibrational frequencies and geometric parameters (bond lengths, bond angles) were calculated using Ab Initio Hartree Fock (HF), Density Functional Theory (B3LYP) methods with 6-311++G(d,p) basis set by Gaussian 09W program. The computed values of frequencies are scaled using a suitable scale factor to yield good coherence with the observed values. The assignments of the vibrational frequencies were performed by potential energy distribution (PED) analysis by using VEDA 4 program. The theoretical optimized geometric parameters and vibrational frequencies were compared with the corresponding experimental X-ray diffraction data, and they were seen to be in a good agreement with each other. Also, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energies were calculated.

Structural and computational study of 1,2,4-triazolin-5-thione derivative and its DMSO solvate

NASA Astrophysics Data System (ADS)

Dybała, Izabela; Wawrzycka-Gorczyca, Irena; Struga, Marta

2017-11-01

The solid state structure of 3-(4-phenyl-5-oxo-1,2,4-triazolin-1-ylmethyl)-4-cyclohexyl-1,2,4-triazolin-5-thione (1) was characterized by FT-IR and X-ray diffraction experiment. Additionally, molecular and crystal structure of its DMSO solvate (1DMSO) has been determined by X-ray diffraction method. The influence of DMSO molecules incorporation to the crystal lattice on geometry of triazolin-5-thione derivative molecule and crystal packing was analyzed. Non-covalent bonds within the crystals are additionally visualized by determination of Hirshfeld surfaces. According to results of conformational analysis in gas, molecule of triazolin-5-thione derivative adopts the lowest energy conformation in 1DMSO crystal. The crystal structure of 1 and 1DMSO were compared with previously described structurally similar compounds, in which the cyclohexyl substituent was replaced by aromatic one (phenyl/methoxyphenyl). Very interesting differences in molecules association were found by comparing the crystal structures of 1 and 1DMSO with their, mentioned above, aromatic derivatives. Interesting properties of triazolin-5-thione derivatives are connected with their π-electron delocalization effects, thus aromaticity of heterocyclic fragments has been investigated by means of the HOMA index. Comparison of aromaticity calculations results with association tendency of molecules shows that triazolin-5-one fragments reach higher aromaticity when nitrogen atom from this moiety acts as a donor in strong Nsbnd H⋯N hydrogen bonds.

Symposium N: Materials and Devices for Thermal-to-Electric Energy Conversion

DTIC Science & Technology

2010-08-24

X - ray diffraction, transmission electron microscopy, scanning electron microscopy, and dynamic light scattering. Thermal conductivity measurements...SEM), X - ray diffraction (XRD) measurements as well as Raman spectroscopy. The results from these techniques indicate a clear modification...was examined by using scanning electron microscope (SEM; HITACHI S-4500 model) attached with an energy dispersive x - ray spectroscopy. The electrical

Inkjet printable-photoactive all inorganic perovskite films with long effective photocarrier lifetimes.

PubMed

Ilie, C C; Guzman, F; Swanson, B L; Evans, I R; Costa, P S; Teeter, J D; Shekhirev, M; Benker, N; Sikich, S; Enders, A; Dowben, P A; Sinitskii, A; Yost, A J

2018-05-10

Photoactive perovskite quantum dot films, deposited via an inkjet printer, have been characterized by x-ray diffraction and x-ray photoelectron spectroscopy. The crystal structure and bonding environment are consistent with CsPbBr 3 perovskite quantum dots. The current-voltage (I-V) and capacitance-voltage (C-V) transport measurements indicate that the photo-carrier drift lifetime can exceed 1 ms for some printed perovskite films. This far exceeds the dark drift carrier lifetime, which is below 50 ns. The printed films show a photocarrier density 10 9 greater than the dark carrier density, making these printed films ideal candidates for application in photodetectors. The successful printing of photoactive-perovskite quantum dot films of CsPbBr 3 , indicates that the rapid prototyping of various perovskite inks and multilayers is realizable.

Adsorption of dodecylamine hydrochloride on graphene oxide in water

NASA Astrophysics Data System (ADS)

Chen, Peng; Li, Hongqiang; Song, Shaoxian; Weng, Xiaoqing; He, Dongsheng; Zhao, Yunliang

Cationic surfactants in water are difficult to be degraded, leading to serious water pollution. In this work, graphene oxide (GO) was used as an adsorbent for removing Dodecylamine Hydrochloride (DACl), a representative cationic surfactant. X-ray diffraction (XRD), FT-IR spectroscopy and atomic force microscope (AFM) were used to characterize the prepared GO. The adsorption of DACl on GO have been investigated through measurements of adsorption capacity, zeta potential, FTIR, and X-ray photoelectron spectroscopy (XPS). The experimental results have shown that the adsorption kinetics could be described as a rate-limiting pseudo second-order process, and the adsorption isotherm agreed well with the Freundlich model. GO was a good adsorbent for DACl removal, compared with coal fly ash and powdered activated carbon. The adsorption process was endothermic, and could be attributed to electrostatic interaction and hydrogen bonding between DACl and GO.

Direct laser sintered WC-10Co/Cu nanocomposites

NASA Astrophysics Data System (ADS)

Gu, Dongdong; Shen, Yifu

2008-04-01

In the present work, the direct metal laser sintering (DMLS) process was used to prepare the WC-Co/Cu nanocomposites in bulk form. The WC reinforcing nanoparticles were added in the form of WC-10 wt.% Co composite powder. The microstructural features and mechanical properties of the laser-sintered sample were characterized by X-ray diffraction (XRD), atomic force microscope (AFM), scanning electron microscope (SEM), energy dispersive X-ray spectroscope (EDX), and nanoindentation tester. It showed that the original nanometric nature of the WC reinforcing particulates was well retained without appreciable grain growth after laser processing. A homogeneous distribution of the WC reinforcing nanoparticles with a coherent particulate/matrix interfacial bonding was obtained in the laser-sintered structure. The 94.3% dense nanocomposites have a dynamic nanohardness of 3.47 GPa and a reduced elastic modulus of 613.42 GPa.

Relationship of microstructure properties to oxygen impurities in nanocrystalline silicon photovoltaic materials

NASA Astrophysics Data System (ADS)

Xu, H.; Wen, C.; Liu, H.; Li, Z. P.; Shen, W. Z.

2013-03-01

We have fully investigated the correlation of microstructure properties and oxygen impurities in hydrogenated nanocrystalline silicon photovoltaic films. The achievement has been realized through a series of different hydrogen dilution ratio treatment by plasma enhanced chemical vapor deposition system. Raman scattering, x-ray diffraction, and ultraviolet-visible transmission techniques have been employed to characterize the physical structural characterization and to elucidate the structure evolution. The bonding configuration of the oxygen impurities was investigated by x-ray photoelectron spectroscopy and the Si-O stretching mode of infrared-transmission, indicating that the films were well oxidized in SiO2 form. Based on the consistence between the proposed structure factor and the oxygen content, we have demonstrated that there are two dominant disordered structure regions closely related to the post-oxidation contamination: plate-like configuration and clustered microvoids.

Molecular beam epitaxial growth and characterization of InSb1 - xNx on GaAs for long wavelength infrared applications

NASA Astrophysics Data System (ADS)

Patra, Nimai C.; Bharatan, Sudhakar; Li, Jia; Tilton, Michael; Iyer, Shanthi

2012-04-01

Recent research progress and findings in InSbN have attracted great attention due to its use in long wavelength infrared applications. A large bandgap reduction in InSb resulting from high N incorporation with minimal crystal defects is challenging due to relatively small atomic size of N. Hence optimization of growth conditions plays an important role in the growth of high-quality InSbN epilayers for device purposes. In this paper, we report on the correlation of structural, vibrational, electrical, and optical properties of molecular beam epitaxially grown InSbN epilayers grown on GaAs substrates, as a function of varying growth temperatures. Two dimensional growths of InSb and InSbN were confirmed from dynamic reflection high energy electron diffraction patterns and growth parameters were optimized. High crystalline quality of the epilayers is attested to by a low full width at half maximum of 200 arcsec from high resolution x-ray diffraction (HRXRD) scans and by the high intensity and well-resolved InSb longitudinal optical (LO) and 2nd order InSb LO mode observed from micro-Raman spectroscopy. The N incorporation in these InSbN epilayers is estimated to be 1.4% based on HRXRD simulation. X-ray photoelectron spectroscopy (XPS) studies reveal that most of the N present in the layers are in the form of In-N bonding. Variation of the lattice disorder with growth temperature is correlated with the types of N bonding present, the carrier concentration and mobility, observed in the corresponding XPS spectra and Hall measurements, respectively. XPS analysis, HRXRD scans, and Raman spectral analysis indicate that lower growth temperature favors In-N bonding which dictates N incorporation in the substitutional sites and lattice disorder, whereas, high growth temperature promotes the formation of In-N-Sb bonding. The best room temperature and 77 K electrical transport parameters and maximum redshift in the absorption edge have been achieved in the InSbN epilayer grown in the 290 °C ˜ 330 °C temperature range.

Solid state and dynamic solution structures of O-carbamidine amidoximes gives further insight into the mechanism of zinc(II)-mediated generation of 1,2,4-oxadiazoles

NASA Astrophysics Data System (ADS)

Kulish, Kirill I.; Novikov, Alexander S.; Tolstoy, Peter M.; Bolotin, Dmitrii S.; Bokach, Nadezhda A.; Zolotarev, Andrey A.; Kukushkin, Vadim Yu.

2016-05-01

Three new iminium salts [H2Ndbnd C(R)ONdbnd C(R‧)NH2](p-TolSO3)·½H2O ([1-3](p-TolSO3)·½H2O; R/R‧ = NMe2/PhCH21, NMe2/p-BrC6H42, N(CH2)5/p-BrC6H43) were synthesized via ZnII-mediated amidoxime-cyanamide coupling and their solid structures were studied by X-ray diffraction. Solution structure and conformational changes of [1-3](p-TolSO3)·½H2O were studied by dynamic NMR. The obtained quantitative data were supported by DFT calculations. All the obtained results help to understand the relative stability of the salts [H2Ndbnd C(R)ONdbnd C(R‧)NH2](X) (R = NAlk2, Alk, Ar) and give a further insight into the mechanism of ZnII-mediated generation of 1,2,4-oxadiazoles. The electron delocalization and sesquialteral bonds in the [H2Ndbnd C(NR2)ONdbnd C(R‧)NH2]+ system was recognized by estimation of values of activation energy barriers (14-18 kcal/mol by DNMR and 16-17 kcal/mol by DFT calculations) for the rotation around the CN bonds for the NR2 groups and inspection of the solid-state X-ray data along with the Wiberg bond indices (intermediate single/double bond order for the CN distances). This electron delocalization is responsible for the stabilization of the positively charged iminium cation. The moderate strength hydrogen bonding between the oxime N atom and the =NH2 group, which is verified from the X-ray, DNMR experiments, and by using quantum chemical calculations, stabilizes the iminium salt, but it is still weak to prevent the heterocyclization. Theoretical calculations of the heterocyclization of [H2Ndbnd C(R)ONdbnd C(R‧)NH2]+ to 1,2,4-oxadiazoles demonstrated that it is kinetically hindered to a greater extent for R = NAlk2 and this explains their lower reactivity as compared to the iminium salts with R = Alk, Ar.

Novel ethylenediamine-gallium phosphate containing 6-fold coordinated gallium atoms with unusual four equatorial Ga–N bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Torre-Fernández, Laura; Espina, Aránzazu; Khainakov, Sergei A.

2014-07-01

A novel ethylenediamine-gallium phosphate, formulated as Ga(H{sub 2}NCH{sub 2}CH{sub 2}NH{sub 2}){sub 2}PO{sub 4}·2H{sub 2}O, was synthesized under hydrothermal conditions. The crystal structure, including hydrogen positions, was determined using single-crystal X-ray diffraction data (monoclinic, a=9.4886(3) Å, b=6.0374(2) Å, c=10.2874(3) Å, and β=104.226(3)°, space group Pc) and the bulk was characterized by chemical (Ga–P–C–H–N) and thermal analysis (TG–MS and DSC), including activation energy data of its thermo-oxidative degradation, powder X-ray diffraction (PXRD), solid-state nuclear magnetic resonance (SS-NMR) measurements, and transmission electron microscopy (TEM, SAED/NBD, and STEM BF-EDX). The crystal structure is built up of infinite zig-zag chains running along the c-axis, formedmore » by vertex-shared (PO{sub 4}) and (GaO{sub 2}N{sub 4}) polyhedra. The new compound is characterized by unusual four equatorial Ga–N bonds coming from two nonequivalent ethylenediamine molecules and exhibits strong blue emission at 430 nm (λ{sub ex}=350 nm) in the solid state at room temperature. - Graphical abstract: Single crystals of a new ethylenediamine-gallium phosphate, Ga(H{sub 2}NCH{sub 2}CH{sub 2}NH{sub 2}){sub 2}PO{sub 4}·2H{sub 2}O, were obtained and the structural features presented. This structure is one of the scarce examples of GaPO with Ga–N bonds reported. - Highlights: • A novel ethylenediamine-gallium phosphate was hydrothermally synthesized. • The new compound is characterized by unusual four equatorial Ga–N bonds. • Void-volume analysis shows cages and channels with sizes ideally suited to accommodate small molecules. • The new compound exhibits strong blue emission.« less

Photomagnetic switching of heterometallic complexes [M(dmf)4(H2O)3(mu-CN)Fe(CN)5].H2O (M=Nd, La, Gd, Y) analyzed by single-crystal X-ray diffraction and ab initio theory.

PubMed

Svendsen, Helle; Overgaard, Jacob; Chevallier, Marie A; Collet, Eric; Chen, Yu-Sheng; Jensen, Frank; Iversen, Bo B

2010-06-25

Single-crystal X-ray diffraction measurements have been carried out on [Nd(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (1; dmf=dimethylformamide), [Nd(dmf)(4)(H(2)O)(3)(mu-CN)Co(CN)(5)].H(2)O (2), [La(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (3), [Gd(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (4), and [Y(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (5), at 15(2) K with and without UV illumination of the crystals. Significant changes in unit-cell parameters were observed for all the iron-containing complexes, whereas 2 showed no response to UV illumination. Photoexcited crystal structures have been determined for 1, 3, and 4 based on refinements of two-conformer models, and excited-state occupancies of 78.6(1), 84(6), and 86.6(7)% were reached, respectively. Significant bond-length changes were observed for the Fe-ligand bonds (up to 0.19 A), the cyano bonds (up to 0.09 A), and the lanthanide-ligand bonds (up to 0.10 A). Ab initio theoretical calculations were carried out for the experimental ground-state geometry of 1 to understand the electronic structure changes upon UV illumination. The calculations suggest that UV illumination gives a charge transfer from the cyano groups on the iron atom to the lanthanide ion moiety, {Nd(dmf)(4)(H(2)O)(3)}, with a distance of approximately 6 A from the iron atom. The charge transfer is accompanied by a reorganization of the spin state on the {Fe(CN)(6)} complex, and a change in geometry that produces a metastable charge-transfer state with an increased number of unpaired electrons, thus accounting for the observed photomagnetic effect.

New process of preparation, X-ray characterisation, structure and vibrational studies of a solid solution LiTiOAs 1-xP xO 4 (0⩽ x⩽1)

NASA Astrophysics Data System (ADS)

Chakir, M.; El Jazouli, A.; Chaminade, J. P.; Bouree, F.; de Waal, D.

2006-01-01

LiTiOAs 1-xP xO 4 (0⩽ x⩽1) compounds have been prepared using solutions of Li, Ti, As and P elements as starting products. Selected compositions have been investigated by powder X-ray or neutrons diffraction analysis, Raman and infrared spectroscopy. The structure of LiTiOAs 1-xP xO 4 ( x=0, 0.5 and 1) samples determined by Rietveld analysis is orthorhombic with Pnma space group. It is formed by a 3D network of TiO 6 octahedra and XO 4 ( X=As 1-xP x) tetrahedra where octahedral cavities are occupied by lithium atoms. TiO 6 octahedra are linked together by corners and form infinite chains along a-axis. Ti atoms are displaced from the centre of octahedral units in alternating short (1.700-1.709 Å) and long (2.301-2.275 Å) Ti-O bonds. Raman and infrared studies confirm the existence of Ti-O-Ti chains. Thermal stability of LiTiOAsO 4 has been reported.

In situ electrochemical high-energy X-ray diffraction using a capillary working electrode cell geometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, Matthias J.; Bedford, Nicholas M.; Jiang, Naisheng

The ability to generate new electrochemically active materials for energy generation and storage with improved properties will likely be derived from an understanding of atomic-scale structure/function relationships during electrochemical events. Here, the design and implementation of a new capillary electrochemical cell designed specifically forin situhigh-energy X-ray diffraction measurements is described. By increasing the amount of electrochemically active material in the X-ray path while implementing low-Zcell materials with anisotropic scattering profiles, an order of magnitude enhancement in diffracted X-ray signal over traditional cell geometries for multiple electrochemically active materials is demonstrated. This signal improvement is crucial for high-energy X-ray diffraction measurementsmore » and subsequent Fourier transformation into atomic pair distribution functions for atomic-scale structural analysis. As an example, clear structural changes in LiCoO 2under reductive and oxidative conditions using the capillary cell are demonstrated, which agree with prior studies. Accurate modeling of the LiCoO 2diffraction data using reverse Monte Carlo simulations further verifies accurate background subtraction and strong signal from the electrochemically active material, enabled by the capillary working electrode geometry.« less

In Situ 3D Coherent X-ray Diffraction Imaging of Shock Experiments: Possible?

NASA Astrophysics Data System (ADS)

Barber, John

2011-03-01

In traditional coherent X-ray diffraction imaging (CXDI), a 2D or quasi-2D object is illuminated by a beam of coherent X-rays to produce a diffraction pattern, which is then manipulated via a process known as iterative phase retrieval to reconstruct an image of the original 2D sample. Recently, there have been dramatic advances in methods for performing fully 3D CXDI of a sample from a single diffraction pattern [Raines et al, Nature 463 214-7 (2010)], and these methods have been used to image samples tens of microns in size using soft X-rays. In this work, I explore the theoretical possibility of applying 3D CXDI techniques to the in situ imaging of the interaction between a shock front and a polycrystal, a far more stringent problem. A delicate trade-off is required between photon energy, spot size, imaging resolution, and the dimensions of the experimental setup. In this talk, I will outline the experimental and computational requirements for performing such an experiment, and I will present images and movies from simulations of one such hypothetical experiment, including both the time-resolved X-ray diffraction patterns and the time-resolved sample imagery.

High spatial resolution X-ray and gamma ray imaging system using diffraction crystals

DOEpatents

Smither, Robert K [Hinsdale, IL

2011-05-17

A method and a device for high spatial resolution imaging of a plurality of sources of x-ray and gamma-ray radiation are provided. The device comprises a plurality of arrays, with each array comprising a plurality of elements comprising a first collimator, a diffracting crystal, a second collimator, and a detector.

XRD, vibrational spectra and quantum chemical studies of an anticancer drug: 6-Mercaptopurine.

PubMed

Kumar, S Suresh; Athimoolam, S; Sridhar, B

2015-07-05

The single crystal of the hydrated anticancer drug, 6-Mercaptopurine (6-MP), has been grown by slow evaporation technique under room temperature. The structure was determined by single crystal X-ray diffraction. The vibrational spectral analysis was carried out using Laser Raman and FT-IR spectroscopy in the range of 3300-100 and 4000-400 cm(-1). The single crystal X-ray studies shows that the crystal packing is dominated by N-H⋯O and O-H⋯N classical hydrogen bonds leading to a hydrogen bonded ensemble. This classical hydrogen bonds were further connected through O-H⋯S hydrogen bond to form two primary ring R4(4)(16) and R4(4)(12) motifs. These two primary ring motifs are interlinked with each other to build a ladder like structure. These ladders are connected through N-H⋯N hydrogen bond along c-axis of the unit cell through chain C(5) motifs. Further, the strength of the hydrogen bonds is studied through vibrational spectral measurements. The shifting of bands due to the intermolecular interactions was also analyzed in the solid crystalline state. Geometrical optimizations of the drug molecule were done by Density Functional Theory (DFT) using the B3LYP function and Hartree-Fock (HF) level with 6-311++G(d,p) basis set. The optimized molecular geometry and computed vibrational spectra are compared with experimental results which show significant agreement. The natural bond orbital (NBO) analysis was carried out to interpret hyperconjugative interaction and intramolecular charge transfer (ICT). The chemical hardness, electro-negativity and chemical potential of the molecule are carried out by HOMO-LUMO plot. In which, the frontier orbitals has lower band gap value indicating the possible pharmaceutical activity of the molecule. Copyright © 2015 Elsevier B.V. All rights reserved.

Photoluminescence studies on Cd(1-x)Zn(x)S:Mn2+ nanocrystals.

PubMed

Sethi, Ruchi; Kumar, Lokendra; Pandey, A C

2009-09-01

Highly monodispersed, undoped and doped with Mn2+, binary and ternary (CdS, ZnS, Cd(1-x)Zn(x)S) compound semiconductor nanocrystals have been synthesized by co-precipitation method using citric acid as a stabilizer. As prepared sample are characterized by X-ray diffraction, Small angle X-ray scattering, Transmission electron microscope, Optical absorption and Photoluminescence spectroscopy, for their optical and structural properties. X-ray diffraction, Small angle X-ray scattering and Transmission electron microscope results confirm the preparation of monodispersed nanocrystals. Photoluminescence studies show a significant blue shift in the wavelength with an increasing concentration of Zn in alloy nanocrystals.

Observation of sagittal X-ray diffraction by surface acoustic waves in Bragg geometry.

PubMed

Vadilonga, Simone; Zizak, Ivo; Roshchupkin, Dmitry; Evgenii, Emelin; Petsiuk, Andrei; Leitenberger, Wolfram; Erko, Alexei

2017-04-01

X-ray Bragg diffraction in sagittal geometry on a Y-cut langasite crystal (La 3 Ga 5 SiO 14 ) modulated by Λ = 3 µm Rayleigh surface acoustic waves was studied at the BESSY II synchrotron radiation facility. Owing to the crystal lattice modulation by the surface acoustic wave diffraction, satellites appear. Their intensity and angular separation depend on the amplitude and wavelength of the ultrasonic superlattice. Experimental results are compared with the corresponding theoretical model that exploits the kinematical diffraction theory. This experiment shows that the propagation of the surface acoustic waves creates a dynamical diffraction grating on the crystal surface, and this can be used for space-time modulation of an X-ray beam.

Observation of sagittal X-ray diffraction by surface acoustic waves in Bragg geometry1

PubMed Central

Vadilonga, Simone; Zizak, Ivo; Roshchupkin, Dmitry; Evgenii, Emelin; Petsiuk, Andrei; Leitenberger, Wolfram; Erko, Alexei

2017-01-01

X-ray Bragg diffraction in sagittal geometry on a Y-cut langasite crystal (La3Ga5SiO14) modulated by Λ = 3 µm Rayleigh surface acoustic waves was studied at the BESSY II synchrotron radiation facility. Owing to the crystal lattice modulation by the surface acoustic wave diffraction, satellites appear. Their intensity and angular separation depend on the amplitude and wavelength of the ultrasonic superlattice. Experimental results are compared with the corresponding theoretical model that exploits the kinematical diffraction theory. This experiment shows that the propagation of the surface acoustic waves creates a dynamical diffraction grating on the crystal surface, and this can be used for space–time modulation of an X-ray beam. PMID:28381976

Probing the accuracy and precision of Hirshfeld atom refinement with HARt interfaced with Olex2.

PubMed

Fugel, Malte; Jayatilaka, Dylan; Hupf, Emanuel; Overgaard, Jacob; Hathwar, Venkatesha R; Macchi, Piero; Turner, Michael J; Howard, Judith A K; Dolomanov, Oleg V; Puschmann, Horst; Iversen, Bo B; Bürgi, Hans-Beat; Grabowsky, Simon

2018-01-01

Hirshfeld atom refinement (HAR) is a novel X-ray structure refinement technique that employs aspherical atomic scattering factors obtained from stockholder partitioning of a theoretically determined tailor-made static electron density. HAR overcomes many of the known limitations of independent atom modelling (IAM), such as too short element-hydrogen distances, r ( X -H), or too large atomic displacement parameters (ADPs). This study probes the accuracy and precision of anisotropic hydrogen and non-hydrogen ADPs and of r ( X -H) values obtained from HAR. These quantities are compared and found to agree with those obtained from (i) accurate neutron diffraction data measured at the same temperatures as the X-ray data and (ii) multipole modelling (MM), an established alternative method for interpreting X-ray diffraction data with the help of aspherical atomic scattering factors. Results are presented for three chemically different systems: the aromatic hydro-carbon rubrene (orthorhombic 5,6,11,12-tetra-phenyl-tetracene), a co-crystal of zwitterionic betaine, imidazolium cations and picrate anions (BIPa), and the salt potassium hydrogen oxalate (KHOx). The non-hydrogen HAR-ADPs are as accurate and precise as the MM-ADPs. Both show excellent agreement with the neutron-based values and are superior to IAM-ADPs. The anisotropic hydrogen HAR-ADPs show a somewhat larger deviation from neutron-based values than the hydrogen SHADE-ADPs used in MM. Element-hydrogen bond lengths from HAR are in excellent agreement with those obtained from neutron diffraction experiments, although they are somewhat less precise. The residual density contour maps after HAR show fewer features than those after MM. Calculating the static electron density with the def2-TZVP basis set instead of the simpler def2-SVP one does not improve the refinement results significantly. All HARs were performed within the recently introduced HARt option implemented in the Olex2 program. They are easily launched inside its graphical user interface following a conventional IAM.

Method for improving x-ray diffraction determinations of residual stress in nickel-base alloys

DOEpatents

Berman, R.M.; Cohen, I.

1988-04-26

A process for improving the technique of measuring residual stress by x-ray diffraction in pieces of nickel-base alloys is discussed. Part of a predetermined area of the surface of a nickel-base alloy is covered with a dispersion. This exposes the covered and uncovered portions of the surface of the alloy to x-rays by way of an x-ray diffractometry apparatus, making x-ray diffraction determinations of the exposed surface, and measuring the residual stress in the alloy based on these determinations. The dispersion is opaque to x-rays and serves a dual purpose, since it masks off unsatisfactory signals such that only a small portion of the surface is measured, and it supplies an internal standard by providing diffractogram peaks comparable to the peaks of the nickel alloy so that the alloy peaks can be very accurately located regardless of any sources of error external to the sample. 2 figs.

Dynamic x-ray imaging of laser-driven nanoplasmas

NASA Astrophysics Data System (ADS)

Fennel, Thomas

2016-05-01

A major promise of current x-ray science at free electron lasers is the realization of unprecedented imaging capabilities for resolving the structure and ultrafast dynamics of matter with nanometer spatial and femtosecond temporal resolution or even below via single-shot x-ray diffraction. Laser-driven atomic clusters and nanoparticles provide an ideal platform for developing and demonstrating the required technology to extract the ultrafast transient spatiotemporal dynamics from the diffraction images. In this talk, the perspectives and challenges of dynamic x-ray imaging will be discussed using complete self-consistent microscopic electromagnetic simulations of IR pump x-ray probe imaging for the example of clusters. The results of the microscopic particle-in-cell simulations (MicPIC) enable the simulation-assisted reconstruction of corresponding experimental data. This capability is demonstrated by converting recently measured LCLS data into a ultrahigh resolution movie of laser-induced plasma expansion. Finally, routes towards reaching attosecond time resolution in the visualization of complex dynamical processes in matter by x-ray diffraction will be discussed.

Infrastructure development for radioactive materials at the NSLS-II

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sprouster, D. J.; Weidner, R.; Ghose, S. K.

2018-02-01

The X-ray Powder Diffraction (XPD) Beamline at the National Synchrotron Light Source-II is a multipurpose instrument designed for high-resolution, high-energy X-ray scattering techniques. In this article, the capabilities, opportunities and recent developments in the characterization of radioactive materials at XPD are described. The overarching goal of this work is to provide researchers access to advanced synchrotron techniques suited to the structural characterization of materials for advanced nuclear energy systems. XPD is a new beamline providing high photon flux for X-ray Diffraction, Pair Distribution Function analysis and Small Angle X-ray Scattering. The infrastructure and software described here extend the existing capabilitiesmore » at XPD to accommodate radioactive materials. Such techniques will contribute crucial information to the characterization and quantification of advanced materials for nuclear energy applications. We describe the automated radioactive sample collection capabilities and recent X-ray Diffraction and Small Angle X-ray Scattering results from neutron irradiated reactor pressure vessel steels and oxide dispersion strengthened steels.« less

Infrastructure development for radioactive materials at the NSLS-II

DOE PAGES

Sprouster, David J.; Weidner, R.; Ghose, S. K.; ...

2017-11-04

The X-ray Powder Diffraction (XPD) Beamline at the National Synchrotron Light Source-II is a multipurpose instrument designed for high-resolution, high-energy X-ray scattering techniques. In this paper, the capabilities, opportunities and recent developments in the characterization of radioactive materials at XPD are described. The overarching goal of this work is to provide researchers access to advanced synchrotron techniques suited to the structural characterization of materials for advanced nuclear energy systems. XPD is a new beamline providing high photon flux for X-ray Diffraction, Pair Distribution Function analysis and Small Angle X-ray Scattering. The infrastructure and software described here extend the existing capabilitiesmore » at XPD to accommodate radioactive materials. Such techniques will contribute crucial information to the characterization and quantification of advanced materials for nuclear energy applications. Finally, we describe the automated radioactive sample collection capabilities and recent X-ray Diffraction and Small Angle X-ray Scattering results from neutron irradiated reactor pressure vessel steels and oxide dispersion strengthened steels.« less