Photochemical reaction pathways of carbon tetrabromide in solution probed by picosecond X-ray diffraction

We report a liquid-phase time-resolved X-ray diffraction study that resolves the molecular structures of the short-lived intermediates formed in the photodissociation of tetrabromomethane in methanol. Time-resolved X-ray diffraction can detect all chemical species simultaneously, and the diffraction signal from each chemical species can be quantitatively calculated from molecular structures and compared with experimental data with high accuracy and precision. The photochemistry of carbon tetrahalides has long been explored to describe their reactions in the natural environment due to its relevance to ozone depletion. Excited with an ultraviolet optical pulse, the complicated photodissociation dynamics of CBr4 was followed in a wide temporal range from picoseconds up to microseconds and associated rate coefficients were determined by analyzing time-resolved diffraction patterns accumulated from 100 ps X-ray pulses. The homolytic cleavage of one C-Br bond in the parent CBr4 molecule yields the CBr3 and Br radicals, which escape from the solvent cage and combine nongeminately to form C2Br6 and Br2, respectively. C2Br6 eventually decays to give C2Br4 and Br2 as final stable products. Our diffraction data at the current signal-to-noise ratio could not provide any evidence for the geminate recombination of the CBr3 and Br radicals to form the Br2CBr-Br isomer or the solvated ion pair, implying that their formation is a minor channel compared with those observed clearly by time-resolved diffraction in this work.     

The Feasibility of Combined NAA and Neutron Diffraction

By employing neutron (or X-ray) diffraction, the structure of crystalline materials can be determined. However, if an impurity in the crystal is present in concentrations below, say, 1·10^–4, its influence cannot be observed in the diffraction patterns. If the impurity present at low concentrations is to be localized, a signal uniquely attributable to the impurity must be obtained. In this paper, two such methods, based on the same principles as the "X-ray standing wave" technique, are proposed for neutrons.     

X-ray diffraction of protein crystal grown in a nano-liter scale droplet in a microchannel and evaluation of its applicability

We describe the technical aspects of the in-situ X-ray diffraction of a protein crystal prepared by a nanodroplet-based crystallization method. We were able to obtain diffraction patterns from a crystal grown in a capillary without any manipulation. Especially in our experimental approach, the crystals that moved to the nanodroplet interface were fixed strongly enough to carry out X-ray diffraction measurements that could be attributed to the high surface tension of the nanodroplet. The crystal was damaged by an indirect action of the X-rays because our in-situ X-ray diffraction measurement was carried out in the liquid phase without freezing the crystal; however, the obtained several diffraction patterns were of sufficiently fine quality for the crystal structure factors to be generated. We consider the technical examination presented in this paper to represent a seamless coupling of crystallization to X-ray analysis.     

Organically templated metal germanate: ionothermal synthesis of (C8H24N4)[NbOGe6O13(OH)2F

A very rare organically templated niobium germanate was synthesized and structurally characterized by single-crystal X-ray diffraction. The crystal shows an intense second harmonic generation signal. It is the first example of the synthesis of organically templated metal germanate using an ionic liquid as a solvent.     

Application of large-area avalanche photodiodes to X-ray spectrometry of muonic atoms

Large-area avalanche photodiodes have been investigated as 1.9-keV X-ray detectors for the muonic hydrogen Lamb-shift experiment. We report experimental tests carried out for evaluation of the avalanche photodiode capabilities for X-ray detection in the intense radiation and low counting rate environment of experiments with muonic atoms. Several muonic atoms were used and it was shown that the electronic background of muonic atom X-ray spectra can be reduced simply by timing the X-ray signal against the gate signal produced by the muon entrance. Furthermore, the background can be eliminated using coincidences between the X-ray signal and the signal resulting from the electron due to the muon decay. This coincidence discrimination results, however, in a reduction of the X-ray detection efficiency.     

Pressure-driven phase transitions in NaBH4: theory and experiments

We have investigated pressure-induced structural transitions in NaBH4 through density-functional theory calculations combined with X-ray and neutron diffraction experiments. Our calculations confirm that the cubic phase is stable up to 5.4 GPa and an orthorhombic phase occurs above 8.9 GPa, as observed in X-ray diffraction experiments. Both the calculations and X-ray diffraction measurements identify an intermediate tetragonal phase that appears between 6 and 8 GPa; that is, between the cubic and orthorhombic phases. This result is also confirmed by high-pressure neutron diffraction experiments performed on NaBD4. Our calculations and X-ray diffraction measurements show that the space group of the orthorhombic phase above 8.9 GPa is Pnma and the orthorhombic phase remains stable up to 30 GPa. The calculated equations of state are in excellent agreement with experiments.     

Picosecond Time Resolved Hard X-Ray Diffraction from Laser Heated Metallic Crystals

We report the development of a novel hard X-ray diffraction system with picosecond time resolution. Picosecond X-ray pulses are produced by excitation of an X-ray diode with picosecond ultraviolet light pulses at a repetition rate of 300 Hz. The X-ray pulses are synchronized to the optical pulses with picosecond accuracy. The system has been utilized in picosecond time resolved X-ray diffraction of laser pulse heated gold and platinum single crystals.     

Probing the pore wall structure of nanoporous carbons using adsorption

Hitherto, adsorption has been traditionally used to study only the porous structure in disordered materials, while the structure of the solid phase skeleton has been probed by crystallographic methods such as X-ray diffraction. Here we show that for carbons density functional theory, suitably adapted to consider heterogeneity of the pore walls, can be reliably used to probe features of the solid structure hitherto accessibly only approximately even by crystallographic methods. We investigate a range of carbons and determine pore wall thickness distributions using argon adsorption, with results corroborated by X-ray diffraction.     

X-ray diffraction from the uniaxial and biaxial nematic phases of bent-core mesogens

X-ray diffraction patterns for the uniaxial and biaxial nematic phases exhibited by rigid bent-core mesogens were calculated using a simple model for the molecular form factor and a modified Lorentzian structure factor. The X-ray diffraction patterns depend strongly on the extent of the alignment of the molecular axes as well as the orientation of molecular planes. The X-ray diffraction can be unequivocally used to identify the biaxial nematic phase, study the uniaxial-biaxial phase transition, and estimate the order parameters of the nematic phase.     

Star-shaped molecule of MnII4O6 core with an St=10 high-spin state. A theoretical and experimental study with XPS, XMCD, and other magnetic methods

We report a comprehensive study of the electronic and magnetic properties of a star-shaped molecule comprising a MnII4O6 core. One feature of this compound is weak magnetic coupling constants compared to other similar polyoxo compounds. This leads to complicated low-lying magnetic states in which the ground state is not well separated from the upper-lying states, yielding a high-spin molecule with a giant magnetic moment of up to 20 microB/formula unit. We apply X-ray diffraction and magnetometry as well as other X-ray spectroscopic techniques, namely, X-ray photoelectron spectroscopy, X-ray magnetic circular dichroism, and X-ray emission spectroscopy. We compare our experimental results with ab initio electronic band structure calculations as well as the localized electronic structure around the Mn2+ ions with charge-transfer multiplet calculations.     

Detection of enzymatic activity by means of a diffraction-based biosensor

We demonstrate here, for the first time, the capability of a diffraction-based sensor to detect enzyme activity and provide a simple measure of enzyme kinetics. Patterned samples of mouse IgG were exposed to the enzyme trypsin and the progress of enzymatic degradation of IgG was followed by measuring the decrease in diffraction signal intensity as a function of time. The diffraction signal intensity decreased exponentially as a function of time over a range of trypsin concentrations from 2–100 g mL^–1. Atomic-force microscope images of the samples before and after exposure to trypsin show that the thickness of patterned protein is greatly reduced by the enzyme action, providing useful insight into the mechanism of signal change for the diffraction sensor.     

Evidence of graphitic AB stacking order of graphite oxides

Graphite oxide (GO) samples were prepared by a simplified Brodie method. Hydroxyl, epoxide, carboxyl, and some alkyl functional groups are present in the GO, as identified by solid-state 13C NMR, Fourier-transform infrared spectroscopy, and X-ray photoemission spectroscopy. Starting with pyrolytic graphite (interlayer separation 3.36 A), the average interlayer distance after 1 h of reaction, as determined by X-ray diffraction, increased to 5.62 A and then increased with further oxidation to 7.37 A after 24 h. A smaller signal in 13C CPMAS NMR compared to that in 13C NMR suggests that carboxyl and alkyl groups are at the edges of the flakes of graphite oxide. Other aspects of the chemical bonding were assessed from the NMR and XPS data and are discussed. AB stacking of the layers in the GO was inferred from an electron diffraction study. The elemental composition of GO prepared using this simplified Brodie method is further discussed.     

Clay pigment structure characterisation as a guide for provenance determination—a comparison between laboratory powder micro-XRD and synchrotron radiation XRD

Application of X-ray diffraction (XRD)-based techniques in the analysis of painted artworks is not only beneficial for indisputable identification of crystal constituents in colour layers, but it can also bring insight in material crystal structure, which can be affected by their geological formation, manufacturing procedure or secondary changes. This knowledge might be helpful for art historic evaluation of an artwork as well as for its conservation. By way of example of kaolinite, we show that classification of its crystal structure order based on XRD data is useful for estimation of its provenance. We found kaolinite in the preparation layer of a Gothic wall painting in a Czech church situated near Karlovy Vary, where there are important kaolin deposits. Comparing reference kaolin materials from eight various Czech deposits, we found that these can be differentiated just according to the kaolinite crystallinity. Within this study, we compared laboratory powder X-ray micro-diffraction (micro-XRD) with synchrotron radiation X-ray diffraction analysing the same real sample. We found that both techniques led to the same results.     

Two-Dimensional Crystallography of Amphiphilic Molecules at the Air–Water Interface

The advent of well-collimated, high-intensity synchrotron X-ray sources and the consequent development of surface-specific X-ray diffraction and fluorescence techniques have recently revolutionized the study of Langmuir monolayers at the air–liquid interface. These methods allowed for the first time the determination of the in-plane and vertical structure of such monolayers with a resolution approaching the atomic level. We briefly describe these methods, including grazing incidence X-ray diffraction, specular reflectivity, Bragg rods, standing waves, and surface fluorescence techniques, and review recent results obtained from them for Langmuir films. The methods have been successfully applied in the elucidation of the structure of crystalline aggregates of amphiphilic molecules such as alcohols, carboxylic acids and their salts, α-amino acids, and phospholipids at the water surface. In addition, it became possible to monitor by diffraction the growth and dissolution of the crystalline self-aggregates as well as structural changes occurring by phase transitions. Furthermore, the surface X-ray methods shed new light on the structure of the underlying ionic layer of attached solvent or solute species. Examples are given where singly or doubly charged ions bound to the two-dimensional (2D) crystal form either an ordered or diffuse counterionic layer. Finally, the surface diffraction methods provide data on transfer of structural information from 2D clusters to 3D single crystals, which had been successfully accomplished by epitaxial-like crystallization both in organic and inorganic crystals.     

Functionalized higher acenes: hexacene and heptacene

We have extended our functionalization strategy for pentacene to the higher acenes hexacene and heptacene. Provided a large enough alkyne substituent is used, these large aromatic rods are both stable and soluble and can be characterized spectroscopically as well as by single-crystal X-ray diffraction.     

Electrochemical intercalation of hydrated cations derived from primary amines into 2H-NbS<Subscript>2</Subscript>

We report the electrochemical intercalation of three cations derived from amines with different chain length, into the layered compound 2H-NbS₂. The intercalation processes were accompanied by ex situ and in situ X-ray diffraction. For in situ analysis, an electrochemical cell was designed for the purpose. The X-ray diffraction experiments show that the intercalation is a complex process, which involves stacking faults and the formation of stages. When the cations are removed, no changes in the final interplanar basal distances occur, suggesting that there are ideal concentrations of intercalated ions that stabilize the phases. Also, based on the X-ray diffraction results we propose a steric arrangement for the hydrated cations into the van der Waals gaps.     

薄膜三重价态锰氧化物的制备与性能

应用偏靶射频磁控溅射方法在SrTiO3(001)单晶衬底上制备了三重价态(Mn3+, Mn4+, Mn5+)锰氧化物薄膜La1-x-yCaxKyMnO3. 这种薄膜具有钙钛矿结构, A位拥有La3＋, Ca2＋和K＋三种离子, 对应的B位为Mn3＋, Mn4＋和Mn5＋三重价态离子共存. 通过18 kW高能X射线衍射仪和D8 X射线面探衍射仪检测证实制备的薄膜为取向多晶薄膜. 原子力扫描图像显示薄膜表面平整, 且随薄膜厚度增加表面平整度起伏增大. 表面光电压测试显示, 该薄膜具有明显的光生电压信号.     

Circular dichroism imaging microscopy: application to enantiomorphous twinning in biaxial crystals of 1,8-dihydroxyanthraquinone

A microscope was constructed for imaging circular dichroism of heterogeneous anisotropic media. To avoid linear biases that are common with electronic circular polarization modulation, we chose a retrogressive solution: mechanical light modulation by rotating a linear polarizer with respect to a quarter wave plate continuously tuned by tilting to the operating wavelength. Our comparatively slow technique succeeds with near-perfect circular input and signal averaging using a CCD camera. We have applied the method to anomalously birefringent crystals of 1,8-dihydroxyanthraquinone that are shown to have intergrown mirror image domains, undetected by X-ray diffraction because the twinning complexity renders differences in anomalous dispersion, already small, unreliable. The origin of the anomalous birefringence and the assignment of the absolute configuration are discussed.     

Analysis of polychromaticity effects in X-ray Talbot interferometer

The influence of polychromaticity of the X-ray source on the performance of an X-ray Talbot interferometer applied for phase-contrast imaging is analyzed through numerical simulations based on the Fresnel diffraction theory. The presented simulation results show that the visibility of the self-image is fairly insensitive to the source polychromaticity and explain why the interferometer could be well combined with polychromatic X-ray sources in recent experiments. Furthermore, the self-image with a high visibility can be obtained under polychromatic illumination even at a high-order fractional Talbot distance. This fact implies that the acquired image quality for phase measurements can be improved, since the primary signal for phase measurement is proportional to the inter-grating distance. Finally, we mention that the results are also valid for Talbot–Lau interferometer and scanning double-grating configuration.     

Understanding the structural properties of a dendrimeric material directly from powder X-ray diffraction data

Complete structure determination of an early-generation dendrimeric material 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. This work represents the first application of modern direct-space techniques for structure determination from powder X-ray diffraction data in the case of a dendrimeric material and paves the way for the future application of this approach to enable complete structure determination of other dendrimeric materials that cannot be prepared as single crystal samples suitable for single crystal X-ray diffraction studies.