I20-EDE-Energy Dispersive EXAFS (EDE)
I20-Scanning-X-ray spectroscopy (XAS/XES)
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Diamond Proposal Number(s):
[17574]
Open Access
Abstract: Deep eutectic solvents (DES) and their hydrated mixtures are used for solvothermal routes towards greener functional nanomaterials. Here we present the first static structural and in situ studies of the formation of iron oxide (hematite) nanoparticles in a DES of choline chloride[thin space (1/6-em)]:[thin space (1/6-em)]urea where xurea = 0.67 (aka. reline) as an exemplar solvothermal reaction, and observe the effects of water on the reaction. The initial speciation of Fe3+ in DES solutions was measured using extended X-ray absorption fine structure (EXAFS), while the atomistic structure of the mixture was resolved from neutron and X-ray diffraction and empirical potential structure refinement (EPSR) modelling. The reaction was monitored using in situ small-angle neutron scattering (SANS), to determine mesoscale changes, and EXAFS, to determine local rearrangements of order around iron ions. It is shown that iron salts form an octahedral [Fe(L)3(Cl)3] complex where (L) represents various O-containing ligands. Solubilised Fe3+ induced subtle structural rearrangements in the DES due to abstraction of chloride into complexes and distortion of H-bonding around complexes. EXAFS suggests the complex forms [–O–Fe–O–] oligomers by reaction with the products of thermal hydrolysis of urea, and is thus pseudo-zero-order in iron. In the hydrated DES, the reaction, nucleation and growth proceeds rapidly, whereas in the pure DES, the reaction initially proceeds quickly, but suddenly slows after 5000 s. In situ SANS and static small-angle X-ray scattering (SAXS) experiments reveal that nanoparticles spontaneously nucleate after 5000 s of reaction time in the pure DES before slow growth. Contrast effects observed in SANS measurements suggest that hydrated DES preferentially form 1D particle morphologies because of choline selectively capping surface crystal facets to direct growth along certain axes, whereas capping is restricted by the solvent structure in the pure DES.
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Jan 2021
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B21-High Throughput SAXS
I04-1-Macromolecular Crystallography (fixed wavelength)
I04-Macromolecular Crystallography
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Diamond Proposal Number(s):
[13587, 18598, 15836]
Open Access
Abstract: The Linker of Nucleoskeleton and Cytoskeleton (LINC) complex mechanically couples cytoskeletal and nuclear components across the nuclear envelope to fulfil a myriad of cellular functions, including nuclear shape and positioning, hearing, and meiotic chromosome movements. The canonical model is that 3:3 interactions between SUN and KASH proteins underlie the nucleocytoskeletal linkages provided by the LINC complex. Here, we provide crystallographic and biophysical evidence that SUN-KASH is a constitutive 6:6 complex in which two constituent 3:3 complexes interact head-to-head. A common SUN-KASH topology is achieved through structurally diverse 6:6 interaction mechanisms by distinct KASH proteins, including zinc-coordination by Nesprin-4. The SUN-KASH 6:6 interface provides a molecular mechanism for the establishment of integrative and distributive connections between 3:3 structures within a branched LINC complex network. In this model, SUN-KASH 6:6 complexes act as nodes for force distribution and integration between adjacent SUN and KASH molecules, enabling the coordinated transduction of large forces across the nuclear envelope.
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Jan 2021
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I10-Beamline for Advanced Dichroism
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Diamond Proposal Number(s):
[11784, 12943, 12958]
Open Access
Abstract: From the perspective of surface science, only the topmost atomic layers usually exhibit physical properties that are different to those of the bulk material, whereas the deeper layers are assumed to be bulk-like and remain largely unexplored. Going beyond conventional diffraction and imaging techniques, we have determined the depth dependence of the full 3D spin structure of magnetic skyrmions below the surface of a bulk Cu2OSeO3 sample using the polarization dependence of resonant elastic x-ray scattering (REXS). While the bulk spin configuration showed the anticipated Bloch type structure, it was found that the skyrmion lattice changes to a Néel twisting (i.e., with a different helicity angle) at the surface within a distance of several hundred nm. The exact surface helicity angle and penetration length of this twist have been determined, revealing the detailed internal structure of the skyrmion tube. It was found that the experimental penetration length of the Néel twisting is 7× longer than the theoretical value given by the ratio of J/D. This indicates that apart from the considered spin interactions, i.e., the Heisenberg exchange interaction J and the Dzyaloshinskii-Moriya interaction D, as well as the Zeeman interaction, other effects must play an important role. The findings suggest that the surface reconstruction of the skyrmion lattice is a universal phenomenon, stemming from the breaking of translational symmetry at the interface.
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Jan 2021
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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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I10-Beamline for Advanced Dichroism
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Diamond Proposal Number(s):
[20182]
Open Access
Abstract: A chiral bobber is a localized three-dimensional magnetization configuration, terminated by a singularity. Chiral bobbers coexist with magnetic skyrmions in chiral magnets, lending themselves to new types of skyrmion-complementary bits of information. However, the on-demand creation of bobbers, as well as their direct observation remained elusive. Here, we introduce a new mechanism for creating a stable chiral bobber lattice state via the proximity of two skyrmion species with comparable size. This effect is experimentally demonstrated in a
Cu
2
OSeO
3
/
[
Ta
/
CoFeB
/
MgO
]
4
heterostructure in which an exotic bobber lattice state emerges in the phase diagram of
Cu
2
OSeO
3
. To unambiguously reveal the existence of the chiral bobber lattice state, we have developed a novel characterization technique, magnetic truncation rod analysis, which is based on resonant elastic x-ray scattering.
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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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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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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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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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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[23480]
Abstract: Although circular helicates can be assembled with a range of labile transition-metal centers, solely “chiral-at-metal” examples (i.e., systems without chiral ligands) and heterometallic (i.e., mixed metal systems, racemic or chiral) circular helicates both remain unexplored. Here, we report on the enantioselective synthesis of a heterometallic (Ir2Zn4) hexameric circular helicate and its elaboration into the corresponding triply interlocked Star of David [2]catenane. The relative inertness of Ir(III) enables enantiospecific synthesis of the hexameric circular helicate using chiral-at-metal building blocks. The resulting Star of David [2]catenane, which is a chiral 6-2-1 link, is formed as a single topological enantiomer. The X-ray crystal structure of the (Ir2Zn4)-catenane shows each of the two 95-atom-long macrocycles entwined around the six metal octahedral metal ions and each other, forming a triply interlocked circular double helix. Two PF6– anions reside above and below the central cavity. The Star of David [2]catenane, both with and without coordinated Zn(II) ions, retains the photophysical properties characteristic of cyclometalated Ir(III) complexes. The synthetic strategy opens up new research directions and opportunities for the assembly of other chiral knots, links, and heterometallic circular helicates.
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Jan 2021
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