Open Access

Show Abstract ▼

Abstract: The Diamond Light Source (DLS) beamline I15-1 measures atomic pair distribution functions (PDF) using scattering of 40-80 keV X-rays. A unique focusing element was needed to condense these X-rays from an initial large cross section (11.0 mm H × 4.2 mm V) into a required spot size of FWHM ≈680 μm (H) × 20 μm (V) at a variable position between the sample and the detector. The large numerical aperture is achieved by coating a silicon substrate over 1 m long with three multilayer stripes of Bragg angle 4.2 mrad. One stripe selects X-rays of each energy 40.0, 65.4, and 76.6 keV. Sixteen piezoelectric bimorph actuators attached to the sides of the mirror substrate adjusted the reflecting surface’s shape. Focal spots of vertical width < 15 µm were obtained at three positions over a 0.92 m range, with fast, easy switching from one focal position to another. Minimized root mean square slope errors were close to 0.5 µrad after subtraction of a uniform curvature. Reflectivity curves taken along each stripe showed consistent high peaks with generally small angular variation of peak positions. This is the first application of a 1 m long multilayer-coated bimorph mirror at a synchrotron beamline. Data collected with its help on a slice of a lithium ion battery’s cathode are presented.

Open Access

Show Abstract ▼

Abstract: X-ray computed tomography and, specifically, time-resolved volumetric tomography data collections (4D datasets) routinely produce terabytes of data, which need to be effectively processed after capture. This is often complicated due to the high rate of data collection required to capture at sufficient time-resolution events of interest in a time-series, compelling the researchers to perform data collection with a low number of projections for each tomogram in order to achieve the desired `frame rate'. It is common practice to collect a representative tomogram with many projections, after or before the time-critical portion of the experiment without detrimentally affecting the time-series to aid the analysis process. For this paper these highly sampled data are used to aid feature detection in the rapidly collected tomograms by assisting with the upsampling of their projections, which is equivalent to upscaling the θ-axis of the sinograms. In this paper, a super-resolution approach is proposed based on deep learning (termed an upscaling Deep Neural Network, or UDNN) that aims to upscale the sinogram space of individual tomograms in a 4D dataset of a sample. This is done using learned behaviour from a dataset containing a high number of projections, taken of the same sample and occurring at the beginning or the end of the data collection. The prior provided by the highly sampled tomogram allows the application of an upscaling process with better accuracy than existing interpolation techniques. This upscaling process subsequently permits an increase in the quality of the tomogram's reconstruction, especially in situations that require capture of only a limited number of projections, as is the case in high-frequency time-series capture. The increase in quality can prove very helpful for researchers, as downstream it enables easier segmentation of the tomograms in areas of interest, for example. The method itself comprises a convolutional neural network which through training learns an end-to-end mapping between sinograms with a low and a high number of projections. Since datasets can differ greatly between experiments, this approach specifically develops a lightweight network that can easily and quickly be retrained for different types of samples. As part of the evaluation of our technique, results with different hyperparameter settings are presented, and the method has been tested on both synthetic and real-world data. In addition, accompanying real-world experimental datasets have been released in the form of two 80 GB tomograms depicting a metallic pin that undergoes corruption from a droplet of salt water. Also a new engineering-based phantom dataset has been produced and released, inspired by the experimental datasets.

Show Abstract ▼

Abstract: Solid-state luminescent materials that possess reversible fluorescence changes toward external multistimuli are of immense interest because of their potential applications in data storage and sensors. While the recent developments in this field are mainly focused on the π-conjugated organic molecules. Herein two polymorphic luminescent ionic liquid (IL)-based stimuli-responsive materials were designed by the supramolecular assemblies of an organic-decorated chlorobismuthate anion and a rotationally flexible imidazolium cation, namely, α (1)/β (2)-[Bmmim][BiCl4(2,2′-bpy)] (Bmmim = 1-butyl-2,3-dimethylimidazolium; 2,2′-bpy = 2,2′-bipyridine). Because of the different conformations of the n-butyl chains on the imidazolium cations, tuning of the supramolecular packing structures as well as luminescent colors for 1 and 2 was realized. Single-crystal X-ray diffraction and Hirshfeld surface analyses disclose that the polymorphism-dependent emission may be attributed to the different weak interactions, especially to the π–π interactions between adjacent [BiCl4(2,2′-bpy)]− anions in two compounds. Additionally, compound 2 could be transformed into 1 spontaneously at ambient conditions, which could be triggered by the moisture in the air. Both of the title compounds could detect NH3 vapor selectively through the luminescence “turn-off” method rapidly and reversibly because of the destruction of intermolecular interactions, indicating their stimuli-responsive property toward NH3.

Open Access

Show Abstract ▼

Abstract: Recent progress has been made in paleontology with respect to resolving pigmentation in fossil material. Morphological identification of fossilized melanosomes has been one approach, while a second methodology using chemical imaging and spectroscopy has also provided critical information particularly concerning eumelanin (black pigment) residue. In this work we develop the chemical imaging methodology to show that organosulfur-Zn complexes are indicators of pheomelanin (red pigment) in extant and fossil soft tissue and that the mapping of these residual biochemical compounds can be used to restore melanin pigment distribution in a 3 million year old extinct mammal species (Apodemus atavus). Synchotron Rapid Scanning X-ray Fluorescence imaging showed that the distributions of Zn and organic S are correlated within this fossil fur just as in pheomelanin-rich modern integument. Furthermore, Zn coordination chemistry within this fossil fur is closely comparable to that determined from pheomelanin-rich fur and hair standards. The non-destructive methods presented here provide a protocol for detecting residual pheomelanin in precious specimens.

Show Abstract ▼

Abstract: The α9 subunit of nicotinic acetylcholine receptors (nAChRs) exists mainly in heteropentameric assemblies with α10. Accumulating data indicate the presence of three different binding sites in α9α10 nAChRs: the α9(+)/α9(−), the α9(+)/α10(−), and the α10(+)/α9(−). The major role of the principal (+) side of the extracellular domain (ECD) of α9 subunit in binding of the antagonists methyllylcaconitine and α-bungarotoxin was shown previously by the crystal structures of the monomeric α9-ECD with these molecules. Here we present the 2.26-Å resolution crystal structure of α9-ECD in complex with α-conotoxin (α-Ctx) RgIA, a potential drug for chronic pain, the first structure reported for a complex between an nAChR domain and an α-Ctx. Superposition of this structure with those of other α-Ctxs bound to the homologous pentameric acetylcholine binding proteins revealed significant similarities in the orientation of bound conotoxins, despite the monomeric state of the α9-ECD. In addition, ligand-binding studies calculated a binding affinity of RgIA to the α9-ECD at the low micromolar range. Given the high identity between α9 and α10 ECDs, particularly at their (+) sides, the presented structure was used as template for molecular dynamics simulations of the ECDs of the human α9α10 nAChR in pentameric assemblies. Our results support a favorable binding of RgIA at α9(+)/α9(−) or α10(+)/α9(−) rather than the α9(+)/α10(−) interface, in accordance with previous mutational and functional data.