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31.
Lithium Insertion Mechanism in Iron-Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis
Dr. Damien Dambournet Dr. Karena W Chapman Dr. Mathieu Duttine Dr. Olaf Borkiewicz Dr. Peter J Chupas Dr. Henri Groult 《ChemistryOpen》2015,4(4):443-447
The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)-type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer-sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF-type electrodes, upon de-lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re-oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties. 相似文献
32.
J. Conrad J. Cohen-Tanugi L. E. Strigari 《Journal of Experimental and Theoretical Physics》2015,121(6):1104-1135
The launch of the gamma-ray telescope Fermi Large Area Telescope (Fermi-LAT) started a pivotal period in indirect detection of dark matter. By outperforming expectations, for the first time a robust and stringent test of the paradigm of weakly interacting massive particles (WIMPs) is within reach. In this paper, we discuss astrophysical targets for WIMP detection and the challenges they present, review the analysis tools which have been employed to tackle these challenges, and summarize the status of constraints on and the claimed detections in the WIMP parameter space. Methods and results will be discussed in comparison to Imaging Air Cherenkov Telescopes. We also provide an outlook on short term and longer term developments. 相似文献
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Crosslinked poly(ethylene oxide) containing siloxanes fabricated through thiol‐ene photochemistry 下载免费PDF全文
Victor A. Kusuma Elliot A. Roth William P. Clafshenkel Steven S. Klara Xu Zhou Surendar R. Venna Erik Albenze David R. Luebke Meagan S. Mauter Richard R. Koepsel Alan J. Russell David Hopkinson Hunaid B. Nulwala 《Journal of polymer science. Part A, Polymer chemistry》2015,53(13):1548-1557
Homogenous amphiphilic crosslinked polymer films comprising of poly(ethylene oxide) and polysiloxane were synthesized utilizing thiol‐ene “ click ” photochemistry. A systematic variation in polymer composition was Carried out to obtain high quality films with varied amount of siloxane and poly(ethylene oxide). These films showed improved gas separation performance with high gas permeabilities with good CO2/N2 selectivity. Furthermore, the resulting films were also tested for its biocompatibility, as a carrier media which allow human adult mesenchymal stem cells to retain their capacity for osteoblastic differentiation after transplantation. The obtained crosslinked films were characterized using differential scanning calorimetry, dynamic mechanical analysis, thermogravimetric analysis, FTIR, Raman‐IR , and small angle X‐ray scattering. The synthesis ease and commercial availability of the starting materials suggests that these new crosslinked polymer networks could find applications in wide range of applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1548–1557 相似文献
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Chris H. Hill Agnete H. Viuff Samantha J. Spratley Stéphane Salamone Stig H. Christensen Randy J. Read Nigel W. Moriarty Henrik H. Jensen Janet E. Deane 《Chemical science》2015,6(5):3075-3086
Krabbe disease is a devastating neurodegenerative disorder characterized by rapid demyelination of nerve fibers. This disease is caused by defects in the lysosomal enzyme β-galactocerebrosidase (GALC), which hydrolyzes the terminal galactose from glycosphingolipids. These lipids are essential components of eukaryotic cell membranes: substrates of GALC include galactocerebroside, the primary lipid component of myelin, and psychosine, a cytotoxic metabolite. Mutations of GALC that cause misfolding of the protein may be responsive to pharmacological chaperone therapy (PCT), whereby small molecules are used to stabilize these mutant proteins, thus correcting trafficking defects and increasing residual catabolic activity in cells. Here we describe a new approach for the synthesis of galacto-configured azasugars and the characterization of their interaction with GALC using biophysical, biochemical and crystallographic methods. We identify that the global stabilization of GALC conferred by azasugar derivatives, measured by fluorescence-based thermal shift assays, is directly related to their binding affinity, measured by enzyme inhibition. X-ray crystal structures of these molecules bound in the GALC active site reveal which residues participate in stabilizing interactions, show how potency is achieved and illustrate the penalties of aza/iminosugar ring distortion. The structure–activity relationships described here identify the key physical properties required of pharmacological chaperones for Krabbe disease and highlight the potential of azasugars as stabilizing agents for future enzyme replacement therapies. This work lays the foundation for new drug-based treatments of Krabbe disease. 相似文献
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