I06-Nanoscience
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Diamond Proposal Number(s):
[23819]
Abstract: Tm
Fe
O
3
(TFO) is a canted antiferromagnet that undergoes a spin reorientation transition (SRT) with temperature between 82 and 94 K in single crystals. In this temperature region, the Néel vector continuously rotates from the crystallographic
c
axis (below 82 K) to the
a
axis (above 94 K). The SRT allows for a temperature control of distinct antiferromagnetic states without the need for a magnetic field, making it apt for applications working at terahertz frequencies. For device applications, thin films of TFO are required as well as an electrical technique for read-out of the magnetic state. Here, we demonstrate that orthorhombic TFO thin films can be grown by pulsed laser deposition and the detection of the SRT in TFO thin films can be accessed by making use of the all-electrical spin Hall magnetoresistance, in good agreement for the temperature range where the SRT occurs in bulk crystals. Our results demonstrate that one can electrically detect the SRT in insulators.
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Jan 2021
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I05-ARPES
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Wujun
Shi
,
Benjamin J.
Wieder
,
Holger L.
Meyerheim
,
Yan
Sun
,
Yang
Zhang
,
Yiwei
Li
,
Lei
Shen
,
Yanpeng
Qi
,
Lexian
Yang
,
Jagannath
Jena
,
Peter
Werner
,
Klaus
Koepernik
,
Stuart
Parkin
,
Yulin
Chen
,
Claudia
Felser
,
B. Andrei
Bernevig
,
Zhijun
Wang
Abstract: Topological physics and strong electron–electron correlations in quantum materials are typically studied independently. However, there have been rapid recent developments in quantum materials in which topological phase transitions emerge when the single-particle band structure is modified by strong interactions. Here we demonstrate that the room-temperature phase of (TaSe4)2I is a Weyl semimetal with 24 pairs of Weyl nodes. Owing to its quasi-one-dimensional structure, (TaSe4)2I also hosts an established charge-density wave instability just below room temperature. We show that the charge-density wave in (TaSe4)2I couples the bulk Weyl points and opens a bandgap. The correlation-driven topological phase transition in (TaSe4)2I provides a route towards observing condensed-matter realizations of axion electrodynamics in the gapped regime, topological chiral response effects in the semimetallic phase, and represents an avenue for exploring the interplay of correlations and topology in a solid-state material.
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Jan 2021
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I04-Macromolecular Crystallography
I24-Microfocus Macromolecular Crystallography
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Abstract: MhsT of Bacillus halodurans is a transporter of hydrophobic amino acids and a homologue of the eukaryotic SLC6 family of Na+‐dependent symporters for amino acids, neurotransmitters, osmolytes, or creatine. The broad range of transported amino acids by MhsT prompted the investigation of the substrate recognition mechanism. Here, we report six new substrate‐bound structures of MhsT, which, in conjunction with functional studies, reveal how the flexibility of a Gly‐Met‐Gly (GMG) motif in the unwound region of transmembrane segment 6 (TM6) is central for the recognition of substrates of different size by tailoring the binding site shape and volume. MhsT mutants, harboring substitutions within the unwound GMG loop and substrate binding pocket that mimick the binding sites of eukaryotic SLC6A18/B0AT3 and SLC6A19/B0AT1 transporters of neutral amino acids, exhibited impaired transport of aromatic amino acids that require a large binding site volume. Conservation of a general (G/A/C)ΦG motif among eukaryotic members of SLC6 family suggests a role for this loop in a common mechanism for substrate recognition and translocation by SLC6 transporters of broad substrate specificity.
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Jan 2021
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[21755, 8786]
Open Access
Abstract: We report four new A-site vacancy ordered thiocyanate double double perovskites,A1–x{Ni[Bi(SCN)6](1–x)/3}, A = K+, NH4+, CH3(NH3)+ (MeNH3+) and C(NH2)3+ (Gua+), includingthe first examples of thiocyanate perovskites containing organic A-site cations. We show, usinga combination of X-ray and neutron diffraction, that the structure of these frameworks dependson the A-site cation, and that these frameworks possess complex vacancy-ordering patterns andcooperative octahedral tilts distinctly different from atomic perovskites. Density functional theorycalculations uncover the energetic origin of these complex orders and allow us to propose asimple rule to predict favoured A-site cation orderings for a given tilt sequence. We use theseinsights, in combination with symmetry mode analyses, to show that these complex orders offera new route to non-centrosymmetric perovskites which render them as excellent candidates forpiezo- and ferroelectric applications.
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Jan 2021
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Open Access
Abstract: The use of metals of nanometer dimensions to enhance and manipulate light-matter interactions for emerging plasmonics-enabled nanophotonic and optoelectronic applications is an interesting yet not highly explored area of research beyond plasmonics. Even more importantly, the concept of an active metal that can undergo an optical nonvolatile transition has not been explored. Here, we demonstrate that antimony (Sb), a pure metal, is optically distinguishable between two programmable states as nanoscale thin films. We show that these states, corresponding to the crystalline and amorphous phases of the metal, are stable at room temperature. Crucially from an application standpoint, we demonstrate both its optoelectronic modulation capabilities and switching speed using single subpicosecond pulses. The simplicity of depositing a single metal portends its potential for use in any optoelectronic application where metallic conductors with an actively tunable state are important.
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Jan 2021
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I15-1-X-ray Pair Distribution Function (XPDF)
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Xiao
Hua
,
Alexander S.
Eggeman
,
Elizabeth
Castillo-martinez
,
Rosa
Robert
,
Harry S.
Geddes
,
Ziheng
Lu
,
Chris J.
Pickard
,
Wei
Meng
,
Kamila M.
Wiaderek
,
Nathalie
Pereira
,
Glenn G.
Amatucci
,
Paul A.
Midgley
,
Karena W.
Chapman
,
Ullrich
Steiner
,
Andrew L.
Goodwin
,
Clare
Grey
Diamond Proposal Number(s):
[17315]
Abstract: Metal fluorides, promising lithium-ion battery cathode materials, have been classified as conversion materials due to the reconstructive phase transitions widely presumed to occur upon lithiation. We challenge this view by studying FeF3 using X-ray total scattering and electron diffraction techniques that measure structure over multiple length scales coupled with density functional theory calculations, and by revisiting prior experimental studies of FeF2 and CuF2. Metal fluoride lithiation is instead dominated by diffusion-controlled displacement mechanisms, and a clear topological relationship between the metal fluoride F− sublattices and that of LiF is established. Initial lithiation of FeF3 forms FeF2 on the particle’s surface, along with a cation-ordered and stacking-disordered phase, A-LixFeyF3, which is structurally related to α-/β-LiMn2+Fe3+F6 and which topotactically transforms to B- and then C-LixFeyF3, before forming LiF and Fe. Lithiation of FeF2 and CuF2 results in a buffer phase between FeF2/CuF2 and LiF. The resulting principles will aid future developments of a wider range of isomorphic metal fluorides.
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Jan 2021
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I03-Macromolecular Crystallography
I04-Macromolecular Crystallography
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Maria-agustina
Rossi
,
Veronica
Martinez
,
Philip
Hinchliffe
,
Maria F.
Mojica
,
Valerie
Castillo
,
Diego M.
Moreno
,
Ryan
Smith
,
Brad
Spellberg
,
George L.
Drusano
,
Claudia
Banchio
,
Robert A.
Bonomo
,
James
Spencer
,
Alejandro J.
Vila
,
Graciela
Mahler
Diamond Proposal Number(s):
[17212]
Open Access
Abstract: Infections caused by multidrug resistant (MDR) bacteria are a major public health threat. Carbapenems are among the most potent antimicrobial agents that are commercially available to treat MDR bacteria. Bacterial production of carbapenem-hydrolysing metallo-β-lactamases (MBLs) challenges their safety and efficacy, with subclass B1 MBLs hydrolysing almost all β-lactam antibiotics. MBL inhibitors would fulfil an urgent clinical need by prolonging the lifetime of these life-saving drugs. Here we report the synthesis and activity of a series of 2-mercaptomethyl-thiazolidines (MMTZs), designed to replicate MBL interactions with reaction intermediates or hydrolysis products. MMTZs are potent competitive inhibitors of B1 MBLs in vitro (e.g., Ki = 0.44 μM vs. NDM-1). Crystal structures of MMTZ complexes reveal similar binding patterns to the most clinically important B1 MBLs (NDM-1, VIM-2 and IMP-1), contrasting with previously studied thiol-based MBL inhibitors, such as bisthiazolidines (BTZs) or captopril stereoisomers, which exhibit lower, more variable potencies and multiple binding modes. MMTZ binding involves thiol coordination to the Zn(II) site and extensive hydrophobic interactions, burying the inhibitor more deeply within the active site than D/L-captopril. Unexpectedly, MMTZ binding features a thioether–π interaction with a conserved active-site aromatic residue, consistent with their equipotent inhibition and similar binding to multiple MBLs. MMTZs penetrate multiple Enterobacterales, inhibit NDM-1 in situ, and restore carbapenem potency against clinical isolates expressing B1 MBLs. Based on their inhibitory profile and lack of eukaryotic cell toxicity, MMTZs represent a promising scaffold for MBL inhibitor development. These results also suggest sulphur–π interactions can be exploited for general ligand design in medicinal chemistry.
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Jan 2021
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I13-2-Diamond Manchester Imaging
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Diamond Proposal Number(s):
[21587]
Open Access
Abstract: Accurate modelling of particle shrinkage during biomass pyrolysis is key to the production of biochars with specific morphologies. Such biochars represent sustainable solutions to a variety of adsorption-dependent environmental remediation challenges. Modelling of particle shrinkage during biomass pyrolysis has heretofore been based solely on theory and ex-situ experimental data. Here we present the first in-situ phase-contrast X-ray imaging study of biomass pyrolysis. A novel reactor was developed to enable operando synchrotron radiography of fixed beds of pyrolysing biomass. Almond shell particles experienced more bulk shrinkage and less change in porosity than did walnut shell particles during pyrolysis, despite their similar composition. Alkaline pretreatment was found to reduce this difference in feedstock behaviour. Ex-situ synchrotron X-ray microtomography was performed to study the effects of pyrolysis on pore morphology. Pyrolysis led to a redistribution of pores away from particle surfaces, meaning newly formed surface area may be less accessible to adsorbates.
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Jan 2021
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[10597]
Abstract: The low carbon content powder metallurgy (PM) 625 alloy were manufactured by vacuum induction gas atomization (VIGA) and hot isostatically pressing (HIP) for marine-based application such as parts in the subsea Xmas tree. Corrosion experiment was performed in simulated deep seawater and subsea oil & gas service environment. The microstructures and properties of low carbon 625 alloy were comparably investigated with that of the as-cast alloy. The results indicated that the dendritic arm spacing (DAS) of the as-cast 625 alloy is 2 orders of magnitude higher than that of the powders, whereas the HIPed alloys possess a fine equiaxed grain structures without dendritic segregation and an average grain size of 14.5μm. No minor phase has been found beside the γ matrix in the original powders with different particle size. The tensile strength of low carbon PM 625 alloy is 26% higher than that of as-cast 625 alloy. PM 625 alloy possesses an excellent corrosion resistant in simulated deep seawater and oil & gas service environment for 30 days.
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Jan 2021
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I11-High Resolution Powder Diffraction
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Open Access
Abstract: TiO2-based powder materials have been widely studied as efficient photocatalysts for water splitting due to their low cost, photo-responsivity, earthly abundance, chemical and thermal stability, etc. In particular, the recent breakthrough of nitrogen-doped TiO2, which enhances the presence of structural defects and dopant impurities at elevated temperatures, exhibits an impressive visible-light absorption for photocatalytic activity. Although their electronic and optical properties have been extensively studied, the structure-activity relationship and photocatalytic mechanism remain ambiguous. Herein, we report an in-depth structural study of rutile, anatase and mixed phases (commercial P25) with and without nitrogen-doping by variable-temperature synchrotron X-ray powder diffraction. We report that an unusual anisotropic thermal expansion of the anatase phase can reveal the intimate relationship between sub-surface oxygen vacancies, nitrogen-doping level and photocatalytic activity. For highly doped anatase, a new cubic titanium oxynitride phase is also identified which provides important information on the fundamental shift in absorption wavelength, leading to excellent photocatalysis using visible light.
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Jan 2021
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