I11-High Resolution Powder Diffraction
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S. A.
Barczak
,
R. J.
Quinn
,
J. E.
Halpin
,
K.
Domosud
,
R. I.
Smith
,
A. R.
Baker
,
E.
Don
,
I.
Forbes
,
K.
Refson
,
D. A.
Maclaren
,
J. W. G.
Bos
Diamond Proposal Number(s):
[14032]
Open Access
Abstract: We outline a strategy to improve the thermoelectric performance of n-type XNiSn based half-Heusler alloys through Cu doping into vacant tetrahedral sites. A comprehensive combination of structural characterisation and modelling is employed to discriminate the competing mechanisms for thermoelectric enhancement. During synthesis a mineralising effect occurs that improves the homogeneity of the alloying elements Ti, Zr and Hf, and promotes grain growth, leading to a doubling of the electron mobility. In the formed materials, Cu is a strong n-type dopant, like Sb, but occupies the interstitial site and strongly enhances phonon scattering without diminishing carrier mobility (in contrast to interstitial Ni). Simultaneous alloying with Ti, Zr and Hf serves to minimise the thermal conductivity via regular mass disorder and strain effects. A best electronic power factor, S2/ρ, of 3.6 mW m−1 K−2 and maximum ZT of 0.8 at 773 K were observed for a Ti0.5Zr0.25Hf0.25NiCu0.025Sn composition, enabling promising device power densities of ∼6 W cm−2 and ∼8% conversion efficiency from a 450 K gradient. These findings are important because they provide new insight into the mechanisms underpinning high ZT in the XNiSn system and indicate a direction for further improvements in thermoelectric performance.
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Nov 2019
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I03-Macromolecular Crystallography
I04-Macromolecular Crystallography
I24-Microfocus Macromolecular Crystallography
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Stefanie
Freitag-pohl
,
Andrius
Jasilionis
,
Maria
Håkansson
,
L. Anders
Svensson
,
Rebeka
Kovačič
,
Martin
Welin
,
Hildegard
Watzlawick
,
Lei
Wang
,
Josef
Altenbuchner
,
Magdalena
Płotka
,
Anna Karina
Kaczorowska
,
Tadeusz
Kaczorowski
,
Eva
Nordberg Karlsson
,
Salam
Al-karadaghi
,
Björn
Walse
,
Arnthór
Aevarsson
,
Ehmke
Pohl
Abstract: As part of the Virus-X Consortium that aims to identify and characterize novel proteins and enzymes from bacteriophages and archaeal viruses, the genes of the putative lytic proteins XepA from Bacillus subtilis prophage PBSX and YomS from prophage SPβ were cloned and the proteins were subsequently produced and functionally characterized. In order to elucidate the role and the molecular mechanism of XepA and YomS, the crystal structures of these proteins were solved at resolutions of 1.9 and 1.3 Å, respectively. XepA consists of two antiparallel β-sandwich domains connected by a 30-amino-acid linker region. A pentamer of this protein adopts a unique dumbbell-shaped architecture consisting of two discs and a central tunnel. YomS (12.9 kDa per monomer), which is less than half the size of XepA (30.3 kDa), shows homology to the C-terminal part of XepA and exhibits a similar pentameric disc arrangement. Each β-sandwich entity resembles the fold of typical cytoplasmic membrane-binding C2 domains. Only XepA exhibits distinct cytotoxic activity in vivo, suggesting that the N-terminal pentameric domain is essential for this biological activity. The biological and structural data presented here suggest that XepA disrupts the proton motive force of the cytoplasmatic membrane, thus supporting cell lysis.
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Nov 2019
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B22-Multimode InfraRed imaging And Microspectroscopy
I11-High Resolution Powder Diffraction
I12-JEEP: Joint Engineering, Environmental and Processing
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Harry G. W.
Godfrey
,
Lydia
Briggs
,
Xue
Han
,
William J. F.
Trenholme
,
Christopher
Morris
,
Mathew
Savage
,
Louis
Kimberley
,
Oxana
Magdysyuk
,
Michael
Drakopoulos
,
Claire A.
Murray
,
Chiu C.
Tang
,
Mark D.
Frogley
,
Gianfelice
Cinque
,
Sihai
Yang
,
Martin
Schroeder
Diamond Proposal Number(s):
[11278]
Open Access
Abstract: Understanding the mechanism of assembly and function of metal-organic frameworks (MOFs) is important for the development of practical materials. Herein, we report a time-resolved diffraction analysis of the kinetics of formation of a robust MOF, MFM-300(Fe), which shows high adsorption capacity for CO2 (9.55 mmol g−1 at 293 K and 20 bar). Applying the Avrami-Erofe’ev and the two-step kinetic Finke-Watzky models to in situ high-energy synchrotron X-ray powder diffraction data obtained during the synthesis of MFM-300(Fe) enables determination of the overall activation energy of formation (50.9 kJ mol−1), the average energy of nucleation (56.7 kJ mol−1), and the average energy of autocatalytic growth (50.7 kJ mol−1). The synthesis of MFM-300(Fe) has been scaled up 1000-fold, enabling the successful breakthrough separations of the CO2/N2 mixture in a packed-bed with a selectivity for CO2/N2 of 21.6. This study gives an overall understanding for the intrinsic behaviors of this MOF system, and we have determined directly the binding domains and dynamics for adsorbed CO2 molecules within the pores of MFM-300(Fe).
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Nov 2019
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I02-Macromolecular Crystallography
I04-Macromolecular Crystallography
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Diamond Proposal Number(s):
[306, 7864]
Open Access
Abstract: Muramidases/lysozymes are important bio-molecules, which cleave the glycan backbone in the peptidoglycan polymer found in bacterial cell walls. The glycoside hydrolase (GH) family 22 C-type lysozyme, from the folivorous bird Opisthocomus hoazin (stinkbird), was expressed in Aspergillus oryzae, and a set of variants was produced. All variants were enzymatically active, including those designed to probe key differences between the Hoatzin enzyme and Hen Egg White lysozyme. Four variants showed improved thermostability at pH 4.7, compared to the wild type. The X-ray structure of the enzyme was determined in the apo form and in complex with chitin oligomers. Bioinformatic analysis of avian GH22 amino acid sequences showed that they separate out into three distinct subgroups (chicken-like birds, sea birds and other birds). The Hoatzin is found in the “other birds” group and we propose that this represents a new cluster of avian upper-gut enzymes.
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Nov 2019
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[19876]
Abstract: The hydrophobic central cavity of a water‐soluble M8L12 cubic coordination cage can accommodate a range of phospho‐diester and phospho‐triester guests such as the insecticide 'dichlorvos' (2,2‐dichlorovinyl dimethyl phosphate) and the chemical warfare agent analogue diisopropyl chlorophosphate. The accumulation of hydroxide ions around the cationic cage surface due to ion‐pairing in solution generates a high local pH around the cage, resulting in catalysed hydrolysis of the phospho‐triester guests. A series of control experiments unexpectedly demonstrates that – in marked contrast to previous cases – it is not necessary for the phospho‐triester substrates to be bound inside the cavity for catalysed hydrolysis to occur. This suggests that catalysis can occur on the exterior surface of the cage as well as the interior surface, with the exterior‐binding catalysis pathway dominating here because of the small binding constants for these phospho‐triester substrates in the cage cavity. These observations suggest that cationic but hydrophobic surfaces could act as quite general catalysts in water by bringing substrates into contact with the surface (via the hydrophobic effect) where there is also a high local concentration of anions (due to ion‐pairing / electrostatic effects).
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Nov 2019
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I03-Macromolecular Crystallography
I24-Microfocus Macromolecular Crystallography
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Pooja
Sharma
,
Robert
Mahen
,
Maxim
Rossmann
,
Jamie E.
Stokes
,
Bryn
Hardwick
,
David J.
Huggins
,
Amy
Emery
,
Dominique L.
Kunciw
,
Marko
Hyvonen
,
David R.
Spring
,
Grahame J.
Mckenzie
,
Ashok R.
Venkitaraman
Diamond Proposal Number(s):
[7141, 9537]
Open Access
Abstract: The human polo-like kinase PLK1 coordinates mitotic chromosome segregation by phosphorylating multiple chromatin- and kinetochore-binding proteins. How PLK1 activity is directed to specific substrates via phosphopeptide recognition by its carboxyl-terminal polo-box domain (PBD) is poorly understood. Here, we combine molecular, structural and chemical biology to identify a determinant for PLK1 substrate recognition that is essential for proper chromosome segregation. We show that mutations ablating an evolutionarily conserved, Tyr-lined pocket in human PLK1 PBD trigger cellular anomalies in mitotic progression and timing. Tyr pocket mutations selectively impair PLK1 binding to the kinetochore phosphoprotein substrate PBIP1, but not to the centrosomal substrate NEDD1. Through a structure-guided approach, we develop a small-molecule inhibitor, Polotyrin, which occupies the Tyr pocket. Polotyrin recapitulates the mitotic defects caused by mutations in the Tyr pocket, further evidencing its essential function, and exemplifying a new approach for selective PLK1 inhibition. Thus, our findings support a model wherein substrate discrimination via the Tyr pocket in the human PLK1 PBD regulates mitotic chromosome segregation to preserve genome integrity.
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Nov 2019
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I22-Small angle scattering & Diffraction
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Abstract: It is now well established that cell membranes are much more than a barrier that separate the cytoplasm from the outside world. Regarding membrane's lipids and their self-assembling, the system is highly complex, for example, the cell membrane needs to adopt different curvatures to be functional. This is possible thanks to the presence of non-lamellar-forming lipids, which tend to curve the membrane. Here, we present the effect of squalane, an apolar isoprenoid molecule, on an archaea-like lipid membrane. The presence of this molecule provokes negative membrane curvature and forces lipids to self-assemble under inverted cubic and inverted hexagonal phases. Such non-lamellar phases are highly stable under a broad range of external extreme conditions, e.g. temperatures and high hydrostatic pressures, confirming that such apolar lipids could be included in the architecture of membranes arising from cells living under extreme environments.
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Nov 2019
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I13-2-Diamond Manchester Imaging
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Diamond Proposal Number(s):
[19367]
Abstract: During CO2 storage in depleted oil fields, under immiscible conditions, CO2 can be trapped in the pore space by capillary forces, providing safe storage over geological times - a phenomenon named capillary trapping. Synchrotron X-ray imaging was used to obtain dynamic three-dimensional images of the flow of the three phases involved in this process - brine, oil and gas (nitrogen) - at high pressure and temperature, inside the pore space of Ketton limestone. First, using continuous imaging of the porous medium during gas injection, performed after waterflooding, we observed chains of multiple displacements between the three phases, caused by the connectivity of the pore space. Then, brine was re-injected and double capillary trapping - gas trapping by oil and oil trapping by brine - was the dominant double displacement event. We computed pore occupancy, saturations, interfacial area, mean curvature and Euler characteristic to elucidate these double capillary trapping phenomena, which lead to a high residual gas saturation. Pore occupancy and saturation results show an enhancement of gas trapping in the presence of both oil and brine, which potentially makes CO2 storage in depleted oil reservoirs attractive, combining safe storage with enhanced oil recovery through immiscible gas injection. Mean curvature measurements were used to assess the capillary pressures between fluid pairs during double displacements and these confirmed the stability of the spreading oil layers observed, which facilitated double capillary trapping. Interfacial area and Euler characteristic increased, indicating lower oil and gas connectivity, due to the capillary trapping events.
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Nov 2019
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I15-1-X-ray Pair Distribution Function (XPDF)
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Diamond Proposal Number(s):
[17685]
Abstract: The structural dynamics of a quasi-one-dimensional (1D) mixed-metal cyanide,
C
u
1
/
3
A
g
1
/
3
A
u
1
/
3
CN
, with intriguing thermal properties is explored. All the current known related compounds with straight-chain structures, such as group 11 cyanides CuCN, AgCN, AuCN, and bimetallic cyanides
M
x
M
′
1
−
x
CN
(
M
,
M
′
=
Cu
, Ag, Au), exhibit 1D negative thermal expansion (NTE) along the chains and positive thermal expansion (PTE) perpendicular to them.
C
u
1
/
3
A
g
1
/
3
A
u
1
/
3
CN
exhibits similar PTE perpendicular to the chains, however PTE, rather than NTE, is also observed along the chains. In order to understand the origin of this unexpected behavior, inelastic neutron scattering measurements were carried out, underpinned by lattice-dynamical density-functional-theory (DFT) calculations. Synchrotron-based pair-distribution-function analysis and
13
C
solid-state nuclear-magnetic-resonance measurements were also performed to build an input structural model for the lattice dynamical study. The results indicate that transverse motions of the metal ions are responsible for the PTE perpendicular to the chains, as is the case for the related group 11 cyanides. However, NTE along the chain due to the tension effect of these transverse motions is not observed. As there are different metal-to-cyanide bond lengths in
C
u
1
/
3
A
g
1
/
3
A
u
1
/
3
CN
, the metals in neighboring chains cannot all be truly coplanar in a straight-chain model. For this system, DFT-based phonon calculations predict small PTE along the chain due to low-energy chain-slipping modes induced by a bond-rotation effect on the weak metallophilic bonds. However the observed PTE is greater than that predicted with the straight-chain model. Small bends in the chain provide an alternative explanation for thermal behavior. These would mitigate the tension effect induced by the transverse motions of the metals and, as temperature increases and the chains move further apart, a straightening could occur resulting in the observed PTE. This hypothesis is further supported by unusual evolution in the phonon spectra, which suggest small changes in local symmetry with temperature.
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Nov 2019
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B21-High Throughput SAXS
Krios I-Titan Krios I at Diamond
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Diamond Proposal Number(s):
[16619, 17773]
Open Access
Abstract: Mucin 5B (MUC5B) has an essential role in mucociliary clearance that protects the pulmonary airways. Accordingly, knowledge of MUC5B structure and its interactions with itself and other proteins is critical to better understand airway mucus biology and improve the management of lung diseases such as asthma, cystic fibrosis, and chronic obstructive pulmonary disease (COPD). The role of an N-terminal multimerization domain in the supramolecular organization of MUC5B has been previously described, but less is known about its C-terminal dimerization domain. Here, using cryogenic electron microscopy (cryo-EM) and small-angle X-ray scattering (SAXS) analyses of recombinant disulfide-linked dimeric MUC5B dimerization domain we identified an asymmetric, elongated twisted structure, with a double globular base. We found that the dimerization domain is more resistant to disruption than the multimerization domain suggesting the twisted structure of the dimerization domain confers additional stability to MUC5B polymers. Size-exclusion chromatography-multiangle light scattering (SEC-MALS), SPR-based biophysical analyses and microscale thermophoresis of the dimerization domain disclosed no further assembly, but did reveal reversible, calcium-dependent interactions between the dimerization and multimerization domains that were most active at acidic pH, suggesting that these domains have a role in MUC5B intragranular organization. In summary, our results suggest a role for the C-terminal dimerization domain of MUC5B in compaction of mucin chains during granular packaging via interactions with the N-terminal multimerization domain. Our findings further suggest that the less stable multimerization domain provides a potential target for mucin depolymerization to remove mucus plugs in COPD and other lung pathologies.
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Nov 2019
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