E02-JEM ARM 300CF
|
Diamond Proposal Number(s):
[20528, 23235]
Abstract: We have investigated the microstructural and crystallographic evolution of nanocrystalline zirconia under heavy ion irradiation using in-situ transmission electron microscopy (TEM) and have studied the atomic configurations of defect clusters using aberration-corrected scanning transmission electron microscopy (STEM). Under heavy ion irradiation the monoclinic-ZrO2 is observed to transform into cubic phase, stabilised by the strain induced by irradiation-induced defect clusters. We suggest that the monoclinic-to-cubic transformation is martensitic in nature with an orientation relationship identified to be (100)m∥(100)c and [001]m∥[001]c. By increasing the damage dose, both the formation of voids and irradiation-induced grain growth were observed. A model for the formation of voids is proposed, taking defect interactions into consideration. The study has also demonstrated that high resolution orientation mapping by transmission Kikuchi diffraction (TKD) combined with in-situ irradiation in a TEM is a powerful method to probe the mechanisms controlling irradiation-induced processes, including grain boundary migration, phase transformations and texture evolution.
|
Oct 2020
|
|
I04-1-Macromolecular Crystallography (fixed wavelength)
|
Diamond Proposal Number(s):
[20147]
Open Access
Abstract: Inositol monophosphatase (IMPase) is inhibited by lithium, which is the most efficacious treatment for bipolar disorder. Several therapies have been approved, or are going through clinical trials, aimed at the replacement of lithium in the treatment of bipolar disorder. One candidate small molecule is ebselen, a selenium-containing antioxidant, which has been demonstrated to produce lithium-like effects both in a murine model and in clinical trials. Here, the crystallization and the first structure of human IMPase covalently complexed with ebselen, a 1.47 Å resolution crystal structure (PDB entry 6zk0), are presented. In the complex with human IMPase, ebselen in a ring-opened conformation is covalently attached to Cys141, a residue located away from the active site. IMPase is a dimeric enzyme and in the crystal structure two adjacent dimers share four ebselen molecules, creating a tetramer with approximate 222 symmetry. In the crystal structure presented in this publication, the active site in the tetramer is still accessible, suggesting that ebselen may function as an allosteric inhibitor or may block the binding of partner proteins.
|
Oct 2020
|
|
I03-Macromolecular Crystallography
|
Open Access
Abstract: In eukaryotes, numerous fundamental processes are controlled by the WAVE regulatory complex (WRC) that regulates cellular actin polymerization, crucial for cell motility, cell–cell adhesion and epithelial differentiation. Actin assembly is triggered by interaction of the small GTPase Rac1 with CYFIP1, a key component of the WRC. Previously known as FAM49B, CYRI-B is a protein that is highly conserved across the Eukaryota and has recently been revealed to be a key regulator of Rac1 activity. Mutation of CYRI-B or alteration of its expression therefore leads to altered actin nucleation dynamics, with impacts on lamellipodia formation, cell migration and infection by intracellular pathogens. In addition, knockdown of CYRI-B expression in cancer cell lines results in accelerated cell proliferation and invasiveness. Here, the structure of Rhincodon typus (whale shark) CYRI-B is presented, which is the first to be reported of any CYRI family member. Solved by X-ray crystallography, the structure reveals that CYRI-B comprises three distinct α-helical subdomains and is highly structurally related to a conserved domain present in CYFIP proteins. The work presented here establishes a template towards a better understanding of CYRI-B biological function.
|
Oct 2020
|
|
E01-JEM ARM 200CF
|
Ruoyu
Xu
,
Jingwei
Xiang
,
Junrun
Feng
,
Xuekun
Lu
,
Zhangxiang
Hao
,
Liqun
Kang
,
Ming
Li
,
Yunsong
Wu
,
Chun
Tan
,
Yiyun
Liu
,
Guanjie
He
,
Dan J. L.
Brett
,
Paul R.
Shearing
,
Lixia
Yuan
,
Yunhui
Huang
,
Feng Ryan
Wang
Diamond Proposal Number(s):
[17559, 19318, 19246, 20643]
Abstract: The lithium-sulfur (Li-S) batteries have high theoretical energy density, exceeding that of the lithium-ion batteries. However, their practical applications are hindered by the capacity decay due to lithium polysulfide shuttle effect and sulfur volume expansion. Here, we design a S@hollow carbon with porous shell/MnOx (S@HCS/MnOx) cathode to accommodate and immobilize sulfur and polysulfides, and develop a non-destructive technique X-ray computed tomography (X-ray CT) to in situ visualize the volume expansion of Li-S cathode. The designed cathode achieves a specific capacity of ~1100 mAh g-1 at 0.2 C with a fade rate of 0.18% per cycle over 300 cycles. The X-ray CT shows that only 16% volume expansion and 70% volume fraction of solid sulfur remaining in the S@HCS/MnOx cathode, superior to the commercial cathode with 40% volume expansion and 5% volume remaining of solid sulfur particles. This is the first reported visualization evidence for the effectiveness of hollow carbon structure in accommodating cathode volume expansion and immobilizing sulfur shuttling. X-ray CT can serve as a powerful in situ tool to trace the active materials and then feedback to the structure design, which helps develop efficient and reliable energy storage systems.
|
Oct 2020
|
|
I03-Macromolecular Crystallography
|
Ivan
Campeotto
,
Francis
Galaway
,
Shahid
Mehmood
,
Lea K.
Barfod
,
Doris
Quinkert
,
Vinayaka
Kotraiah
,
Timothy W.
Phares
,
Katherine E.
Wright
,
Ambrosius P.
Snijders
,
Simon J.
Draper
,
Matthew K.
Higgins
,
Gavin J.
Wright
Diamond Proposal Number(s):
[23459]
Open Access
Abstract: Plasmodium falciparum RH5 is a secreted parasite ligand that is essential for erythrocyte invasion through direct interaction with the host erythrocyte receptor basigin. RH5 forms a tripartite complex with two other secreted parasite proteins, CyRPA and RIPR, and is tethered to the surface of the parasite through membrane-anchored P113. Antibodies against RH5, CyRPA, and RIPR can inhibit parasite invasion, suggesting that vaccines containing these three components have the potential to prevent blood-stage malaria. To further explore the role of the P113-RH5 interaction, we selected monoclonal antibodies against P113 that were either inhibitory or noninhibitory for RH5 binding. Using a Fab fragment as a crystallization chaperone, we determined the crystal structure of the RH5 binding region of P113 and showed that it is composed of two domains with structural similarities to rhamnose-binding lectins. We identified the RH5 binding site on P113 by using a combination of hydrogen-deuterium exchange mass spectrometry and site-directed mutagenesis. We found that a monoclonal antibody to P113 that bound to this interface and inhibited the RH5-P113 interaction did not inhibit parasite blood-stage growth. These findings provide further structural information on the protein interactions of RH5 and will be helpful in guiding the development of blood-stage malaria vaccines that target RH5.
|
Oct 2020
|
|
I13-2-Diamond Manchester Imaging
|
Diamond Proposal Number(s):
[16668]
Abstract: Digital volume correlation of in situ synchrotron X-ray computed tomographs has been used to measure the three-dimensional displacement fields around quasi-static propagating cracks in neutron irradiated and unirradiated graphite in specimens of the double cleavage drilled compression geometry. The crack tip location and crack opening were extracted from the displacement fields using a phase congruency edge detection method as cracks were propagated over ∼5 mm. The cracks propagated in mode I, maintaining a constant crack opening angle that was ∼50% smaller for the irradiated graphite. 3D finite element simulations, using the measured full field displacements as boundary conditions, obtained the critical elastic strain energy release rate for crack propagation by calculation of the domain contour J-integral. When the non-linear properties of unirradiated graphite were considered, the strain energy release rate for propagation was constant (180 ± 22 Jm-2) with increasing crack length. The irradiated graphite (fluence of 19.7 × 1020 neutrons cm−2 or 2.6 dpa, 4% weight loss by radiolytic oxidation) had linear elastic properties, and the strain energy release rate for propagation increased linearly from 118 ± 12Jm-2 to 485 ± 75 Jm-2 with crack length.
|
Oct 2020
|
|
I05-ARPES
|
Georg
Poelchen
,
Susanne
Schulz
,
Max
Mende
,
Monika
Guttler
,
Alexander
Generalov
,
Alexander V.
Fedorov
,
Nubia
Caroca-canales
,
Christoph
Geibel
,
Kristin
Kliemt
,
Cornelius
Krellner
,
Steffen
Danzenbacher
,
Dmitry Y.
Usachov
,
Pavel
Dudin
,
Victor N.
Antonov
,
James W.
Allen
,
Clemens
Laubschat
,
Kurt
Kummer
,
Yuri
Kucherenko
,
Denis V.
Vyalikh
Diamond Proposal Number(s):
[17761, 24339]
Open Access
Abstract: Ultra-violet angle-resolved photoemission spectroscopy (UV-ARPES) was used to explore the temperature dependence of the Ce-4f spectral responses for surface and bulk in the antiferromagnetic Kondo lattice CeRh2Si2. Spectra were taken from Ce- and Si-terminated surfaces in a wide temperature range, and reveal characteristic 4f patterns for weakly (surface) and strongly (bulk) hybridized Ce, respectively. The temperature dependence of the Fermi level peak differs strongly for both cases implying that the effective Kondo temperature at the surface and bulk can be rather distinct. The greatly reduced crystal–electric-field (CEF) splitting at the surface gives reason to believe that the surface may exhibit a larger effective Kondo temperature because of a higher local-moment effective degeneracy. Further, the hybridization processes could strongly affect the 4f peak intensity at the Fermi level. We derived the k-resolved dispersion of the Kondo peak which is also found to be distinct due to different sets of itinerant bands to which the 4f states of surface and bulk Ce are coupled. Overall our study brings into reach the ultimate goal of quantitatively testing many-body theories that link spectroscopy and transport properties, for both the bulk and the surface, separately. It also allows for a direct insight into the broader problem of Kondo lattices with two different local-moment sublattices, providing some understanding of why the cross-talking between the two Kondo effects is weak.
|
Oct 2020
|
|
|
|
Open Access
Abstract: Trypanosoma cruzi is the etiologic agent of Chagas disease, which affects over seven million people, especially in developing countries. Undesirable side effects are frequently associated with current therapies, which are typically ineffective in the treatment of all stages of the disease. Here, we report the first synthesis of the neolignan dehydrodieugenol B, a natural product recently shown to exhibit activity against T. cruzi. Using this strategy, a series of synthetic analogues were prepared to explore structure–activity relationships. The in vitro antiparasitic activities of these analogues revealed a wide tolerance of modifications and substituent deletions, with maintained or improved bioactivities against the amastigote forms of the parasite (50% inhibitory concentration (IC50) of 4–63 μM) and no mammalian toxicity (50% cytotoxic concentration (CC50) of >200 μM). Five of these analogues meet the Drugs for Neglected Disease Initiative (DNDi) “hit criteria” for Chagas disease. This work has enabled the identification of key structural features of the natural product and sites where scaffold modification is tolerated.
|
Oct 2020
|
|
B16-Test Beamline
I15-Extreme Conditions
|
Diamond Proposal Number(s):
[17704, 17707]
Open Access
Abstract: Purpose: Photon-counting silicon strip detectors are attracting interest for use in next-generation CT scanners. For CT detectors in a clinical environment, it is desirable to have a low power consumption. However, decreasing the power consumption leads to higher noise. This is particularly detrimental for silicon detectors, which require a low noise floor to obtain a good dose efficiency. The increase in noise can be mitigated using a longer shaping time in the readout electronics. This also results in longer pulses, which requires an increased deadtime, thereby degrading the count-rate performance. However, as the photon flux varies greatly during a typical CT scan, not all projection lines require a high count-rate capability. We propose adjusting the shaping time to counteract the increased noise that results from decreasing the power consumption.
Approach: To show the potential of increasing the shaping time to decrease the noise level, synchrotron measurements were performed using a detector prototype with two shaping time settings. From the measurements, a simulation model was developed and used to predict the performance of a future channel design.
Results: Based on the synchrotron measurements, we show that increasing the shaping time from 28.1 to 39.4 ns decreases the noise and increases the signal-to-noise ratio with 6.5% at low count rates. With the developed simulation model, we predict that a 50% decrease in power can be attained in a proposed future detector design by increasing the shaping time with a factor of 1.875.
Conclusion: Our results show that the shaping time can be an important tool to adapt the pulse length and noise level to the photon flux and thereby optimize the dose efficiency of photon-counting silicon detectors.
|
Oct 2020
|
|
E02-JEM ARM 300CF
|
Diamond Proposal Number(s):
[16967]
Abstract: Single atom catalysts (SACs) are ideal model systems in catalysis research. Here we employ SACs to address the fundamental catalytic challenge of generating well-defined active metal centers to elucidate their interactions with coordinating atoms, which define their catalytic performance. We introduce a soft-landing molecular strategy for tailored SACs based on metal phthalocyanines (MPcs, M = Ni, Co, Fe) on graphene oxide (GO) layers to generate well-defined model targets for mechanistic studies. The formation of electronic channels through π–π conjugation with the graphene sheets enhances the MPc-GO performance in both oxygen evolution and reduction reactions (OER and ORR). Density functional theory (DFT) calculations unravel that the outstanding ORR activity of FePc-GO among the series is due to the high affinity of Fe atoms toward O2 species. Operando X-ray absorption spectroscopy and DFT studies demonstrate that the OER performance of the catalysts relates to thermodynamic or kinetic control at low- or high-potential ranges, respectively. We furthermore provide evidence that the participation of ligating N and C atoms around the metal centers provides a wider selection of active OER sites for both NiPc-GO and CoPc-GO. Our strategy promotes the understanding of coordination–activity relationships of high-performance SACs and their optimization for different processes through tailored combinations of metal centers and suitable ligand environments.
|
Oct 2020
|
|
