85 research outputs found

    The Charge-Transfer Motif in Crystal Engineering. Self-Assembly of Acentric (Diamondoid) Networks from Halide Salts and Carbon Tetrabromide as Electron-Donor/Acceptor Synthons

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    Unusual strength and directionality for the charge-transfer motif (established in solution) are shown to carry over into the solid state by the facile synthesis of a series of robust crystals of the [1:1] donor/acceptor complexes of carbon tetrabromide with the electron-rich halide anions (chloride, bromide, and iodide). X-ray crystallographic analyses identify the consistent formation of diamondoid networks, the dimensionality of which is dictated by the size of the tetraalkylammonium counterion. For the tetraethylammonium bromide/carbon tetrabromide dyad, the three-dimensional (diamondoid) network consists of donor (bromide) and acceptor (CBr4) nodes alternately populated to result in the effective annihilation of centers of symmetry in agreement with the sphaleroid structural subclass. Such inherently acentric networks exhibit intensive nonlinear optical properties in which the second harmonics generation in the extended charge-transfer system is augmented by the effective electronic (HOMO−LUMO) coupling between contiguous CBr4/halide centers

    Ex-situ and in-situ investigations of thermal anti-oxidation treatments of stainless steels by reflection mode EXAFS

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    Different thermal treatments were performed for the anti-oxidation of steel surfaces, and the processes were investigated ex-situ and in-situ by surface sensitive reflection mode EXAFS experiments at the Cr and Fe K-edges. While the samples for the ex-situ studies were heat-treated in a conveyor belt furnace at temperatures between 600 and 900 °C in inert carrier gases (N2 or Ar) using different additives such as hydrogen (H2) and monosilane (SiH4), the in- situ anti-oxidation treatments have been performed in a high vacuum environment (p < 10-6 mbar). While the ex-situ experiments suggest that SiH4-additives are needed for the reduction of the steel to a metallic state, the in-vacuum treatments appear successful for temperatures above approx. 900 °C.DFG/FR 1388/8-1DFG/Ma 1175/48-

    Effect of the water depth on the hydrogen content in SMAW wet welded joints

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    Hydrogen-induced cold cracking is a huge challenge in underwater wet welding. In the present study, the influence of water depth on the diffusible and residually stored hydrogen content is investigated for the case of underwater wet shielded metal arc welding. The welding is carried out in a simulated water depth of 5, 20, 40, and 60 m with four stick electrodes specifically developed for underwater wet welding. The influence of the welding current, the arc voltage and the electrode’s composition on the diffusible hydrogen content are considered. To obtain reproducible welding conditions, a fully automated multi-axis welding system is used inside a pressure chamber. The water depth is simulated by setting the internal pressure up to 6 bar, equivalent to 60 m water depth. A large amount of samples are analysed and statistical method are used to evaluate the results. The results show a significant reduction of the diffusible hydrogen and an increase of residual hydrogen in the joining zone with increasing water depth

    Quantitative dual-energy CT as a nondestructive tool to identify indicators for fossilized bone in vertebrate paleontology

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    Dual-energy computed tomography (DECT) is an imaging technique that combines nondestructive morphological cross-sectional imaging of objects and the quantification of their chemical composition. However, its potential to assist investigations in paleontology has not yet been explored. This study investigates quantitative DECT for the nondestructive density- and element-based material decomposition of fossilized bones. Specifically, DECT was developed and validated for imaging-based calcium and fluorine quantification in bones of five fossil vertebrates from different geological time periods and of one extant vertebrate. The analysis shows that DECT material maps can differentiate bone from surrounding sediment and reveals fluorine as an imaging marker for fossilized bone and a reliable indicator of the age of terrestrial fossils. Moreover, the jaw bone mass of Tyrannosaurus rex showed areas of particularly high fluorine concentrations on DECT, while conventional CT imaging features supported the diagnosis of chronic osteomyelitis. These findings highlight the relevance of radiological imaging techniques in the natural sciences by introducing quantitative DECT imaging as a nondestructive approach for material decomposition in fossilized objects, thereby potentially adding to the toolbox of paleontological studies

    Additive effect of anti-citrullinated protein antibodies and rheumatoid factor on bone erosions in patients with RA

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    Objective To determine whether there is an additive effect of anticitrullinated protein antibodies (ACPA) and rheumatoid factor (RF) on the number and size of bone erosions in patients with rheumatoid arthritis (RA) Methods 242 patients with RA received high-resolution peripheral quantitative CT (HR-pQCT) scans of the metacarpophalangeal joints. Demographic and disease-specific parameters including ACPA and RF levels were recorded from all patients. Erosion numbers and their size were assessed in 238 patients at 714 individual joints (MCP 2, 3 and 4) and 5712 sites (each 4 quadrants in metacarpal heads and phalangeal bases). The volume of erosions was calculated by a semiellipsoid formula. Results Of the 238 patients, 112 patients showed RF and ACPAs (ACPAs+RF+), 28 only RF (RF+), 29 only ACPAs (ACPA+) and 69 were antibody negative (NEG). Erosion number and size were highest in RF+ACPAs+ patient group with significant differences compared with NEG patients with respect to erosion number (p=0.001) and to ACPA-negative patients with respect to erosion size (p<0.001). Results maintained significance in a linear mixed model showing ACPAs+RF+ status and disease duration being associated with higher number (p=0.017 and p=0.005, respectively), and larger size (p=0.014 and p=0.013, respectively) of bone erosions. Furthermore, erosion size was influenced by the presence and titre of RF only in ACPA-positive patients with RA but not in ACPA-negative patients. Conclusions ACPAs and RF show an additive effect on erosion number and erosion size. Concomitant presence of ACPAs and RF is associated with higher erosive disease burden in patients with RA. Furthermore, RF influences erosion size only in ACPA-positive but not in ACPA-negative patients

    Bow-tie optical antenna probes for single-emitter scanning near-field optical microscopy

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    A method for the fabrication of bow-tie optical antennas at the apex of pyramidal Si3N4 atomic force microscopy tips is described. We demonstrate that these novel optical probes are capable of sub-wavelength imaging of single quantum dots at room temperature. The enhanced and confined optical near-field at the antenna feed gap leads to locally enhanced photoluminescence (PL) of single quantum dots. Photoluminescence quenching due to the proximity of metal is found to be insignificant. The method holds promise for single quantum emitter imaging and spectroscopy at spatial resolution limited by the engineered antenna gap width exclusively

    PBX1 is dispensable for neural commitment of RA-treated murine ES cells

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    Experimentation with PBX1 knockout mice has shown that PBX1 is necessary for early embryogenesis. Despite broad insight into PBX1 function, little is known about the underlying target gene regulation. Utilizing the Cre–loxP system, we targeted a functionally important part of the homeodomain of PBX1 through homozygous deletion of exon-6 and flanking intronic regions leading to exon 7 skipping in embryonic stem (ES) cells. We induced in vitro differentiation of wild-type and PBX1 mutant ES cells by aggregation and retinoic acid (RA) treatment and compared their profiles of gene expression at the ninth day post-reattachment to adhesive media. Our results indicate that PBX1 interactions with HOX proteins and DNA are dispensable for RA-induced ability of ES to express neural genes and point to a possible involvement of PBX1 in the regulation of imprinted genes

    Broadening Exposure to Socio-Political Opinions via a Pushy Smart Home Device

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    Motivated by the effects of the filter bubble and echo chamber phenomena on social media, we developed a smart home device, Spkr, that unpredictably “pushes” socio-political discussion topics into the home. The device utilised trending Twitter discussions, categorised by their socio-political alignment, to present people with a purposefully assorted range of viewpoints. We deployed Spkr in 10 homes for 28 days with a diverse range of participants and interviewed them about their experiences. Our results show that Spkr presents a novel means of combating selective exposure to socio-political issues, providing participants with identifiably diverse viewpoints. Moreover, Spkr acted as a conversational prompt for discussion within the home, initiating collective processes and engaging those who would not often be involved in political discussions. We demonstrate how smart home assistants can be used as a catalyst for provocation by altering and pluralising political discussions within households

    The Science Performance of JWST as Characterized in Commissioning

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    This paper characterizes the actual science performance of the James Webb Space Telescope (JWST), as determined from the six month commissioning period. We summarize the performance of the spacecraft, telescope, science instruments, and ground system, with an emphasis on differences from pre-launch expectations. Commissioning has made clear that JWST is fully capable of achieving the discoveries for which it was built. Moreover, almost across the board, the science performance of JWST is better than expected; in most cases, JWST will go deeper faster than expected. The telescope and instrument suite have demonstrated the sensitivity, stability, image quality, and spectral range that are necessary to transform our understanding of the cosmos through observations spanning from near-earth asteroids to the most distant galaxies.Comment: 5th version as accepted to PASP; 31 pages, 18 figures; https://iopscience.iop.org/article/10.1088/1538-3873/acb29
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