I12-JEEP: Joint Engineering, Environmental and Processing
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Diamond Proposal Number(s):
[26476]
Abstract: Two new multicomponent crystalline phases of fenbendazole (FNB), a benzimidazole-based anthelmintic drug, with maleic and oxalic acids have been obtained, and their structural and physicochemical properties carefully investigated. The crystal structures of the solid forms have been determined from powder X-ray diffraction data. The positions of dynamic hydrogen atoms have been further refined via dispersion-corrected density functional theory calculations, which validated the salt nature of the resulting solid forms by demonstrating proton transport from the corresponding acids to the FNB molecule. The in vitro dissolution performance of the solid forms in aqueous media at different pH values, as well as the in vivo anthelmintic efficacy of fenbendazole on the laboratory model of Trichinella spiralis infection in mice have been evaluated and compared to that of the previously reported salt of FNB with p-toluenesulfonic acid. A relationship between the in vitro dissolution characteristics and the in vivo therapeutic action has been revealed and discussed.
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Feb 2023
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I15-1-X-ray Pair Distribution Function (XPDF)
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Mohamed. A.
Ali
,
Wessel M. W.
Winters
,
Moushira A.
Mohamed
,
Dezhi
Tan
,
Guojun
Zheng
,
Rasmus S. K.
Madsen
,
Oxana V.
Magdysyuk
,
Maria
Diaz-Lopez
,
Biao
Cai
,
Nan
Gong
,
Yijue
Xu
,
Ivan
Hung
,
Zhehong
Gan
,
Sabyasachi
Sen
,
Hong-Tao
Sun
,
Thomas D.
Bennett
,
Xiaofeng
Liu
,
Yuanzheng
Yue
,
Jianrong
Qiu
Diamond Proposal Number(s):
[30401]
Abstract: Glassy metal coordination compounds (MCC) [e.g., metal-organic framework (MOF), coordination polymer, and metal inorganic-organic complex (MIOC)] are emerging members of the hybrid glass family. So far, a limited number of crystalline MCCs can be converted into glasses by the melt-quenching. Here, we report a universal wet-chemistry method, by which the super-sized supramolecular MIOC glasses can be synthesized from non-meltable MOFs. Alcohol and acid were used as agents to inhibit crystallization. The MIOC glasses demonstrate unique features including high transparency, shaping capability, and anisotropic network. Directional photoluminescence with a large polarization ratio (~47%) was observed from samples doped with organic dyes. This crystallization-suppressing approach enables fabrication of MCC glasses, which cannot be achieved by conventional vitrification methods, and thus allows for exploring new MCC glasses possessing photonic functionalities.
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Feb 2023
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I12-JEEP: Joint Engineering, Environmental and Processing
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Dominic
Spencer-Jolly
,
Varnika
Agarwal
,
Christopher
Doerrer
,
Bingkun
Hu
,
Shengming
Zhang
,
Dominic L. R.
Melvin
,
Hui
Gao
,
Xiangwen
Gao
,
Paul
Adamson
,
Oxana
Magdysyuk
,
Patrick S.
Grant
,
Robert A.
House
,
Peter G.
Bruce
Diamond Proposal Number(s):
[26082]
Open Access
Abstract: Ag-carbon composite interlayers have been reported to enable Li-free (anodeless) cycling of solid-state batteries. Here, we report structural changes in the Ag-graphite interlayer, showing that on charge, Li intercalates electrochemically into graphite, subsequently reacting chemically with Ag to form Li-Ag alloys. Discharge is not the reverse of charge but rather passes through Li-deficient Li-Ag phases. At higher charging rates, Li intercalation into graphite outpaces the chemical reactions with Ag, delaying the formation of the Li-Ag phases and resulting in more Li metal deposition at the current collector. At and above 2.5 mA·cm−2, Li dendrites are not suppressed. Ag nanoparticles do not suppress dendrites more effectively than does an interlayer of graphite alone. Instead, Ag in the carbon interlayer results in more homogeneous Li and Li-Ag formation on the current collector during charge.
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Feb 2023
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I12-JEEP: Joint Engineering, Environmental and Processing
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Open Access
Abstract: Despite being one of the most thoroughly characterised molecular crystals, hexamethylenetetramine (HMT) and its deuterated counterpart (DHMT), are still not fully understood, especially regarding anharmonic and nuclear quantum effects. In this work, an unprecedented combination of experimental techniques, including neutron and X-ray diffraction, inelastic neutron scattering, neutron transmission, and Compton scattering, all augmented ab initio by harmonic lattice dynamics calculations, was applied. The main question that motivated the presented work was the interplay between the phonon anharmonicity and isotope and nuclear quantum effects related to the zero-point energies of proton and deuteron. Signatures of the combined effects of isotopic substitution, temperature, anharmonicity and nuclear quantum effects were found in data from all experimental methods. In the case of neutron and X-ray diffraction, these signatures manifested as systematic discrepancies between the structural and atomic displacement parameters and thermal diffuse scattering obtained from harmonic lattice calculations and their experimental counterparts. To this end, an important effect was found that could not have been explained by the harmonic lattice modelling; the reverse Ubbelohde effect, i.e. the observation that deuteration decreases hydrogen bond length in HMT. In the case of neutron transmission, further discrepancies between theoretical predictions and experimental data were found at cryogenic temperatures. Finally, applying the diabatic theory of the local potential of the intermolecular hydrogen bond in HMT, it was possible to elucidate the degree of anharmonicity of the C–H···N bonds by relating it to the magnitude of the vibrational isotope effect for the C–H bond stretching observed in inelastic and neutron Compton scattering experiments. It was found that the combined nuclear quantum and anharmonic effects of the protons (deuterons) in hydrogen bonds in HMT (DHMT) manifest as systematic discrepancies between the ab initio predictions for the widths of nuclear momentum distributions and the experimental values.
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Jan 2023
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Abstract: Crystal engineering has, so far, exclusively focused on the development of advanced materials based on small organic molecules. We demonstrate how the cocrystallization of a polymer significantly enhances its thermal stability without compromising its mechanical flexibility, while isomorphous replacement of one of the cocrystal components enables the formation of solid solutions with melting points that can be readily fine-tuned over a practically wide temperature range. The results of this study credibly extend the scope of crystal engineering and cocrystallization from small molecules to polymers.
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Jan 2023
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I12-JEEP: Joint Engineering, Environmental and Processing
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Chu Lun Alex
Leung
,
Matthew D.
Wilson
,
Thomas
Connolley
,
Stephen P.
Collins
,
Oxana V.
Magdysyuk
,
Matthieu N.
Boone
,
Kosuke
Suzuki
,
Matthew C.
Veale
,
Enzo
Liotti
,
Frederic
Van Assche
,
Andrew
Lui
,
Chun
Huang
Diamond Proposal Number(s):
[23400]
Open Access
Abstract: Increasing electrode thickness is gaining more attention as a potential route to increase energy density for Li ion batteries although the realizable capacity and rate capability are usually limited by Li+ ion diffusion during (dis)charge, especially at increased (dis)charge rates. It remains challenging to visualize and quantify the low atomic number Li+ chemical stoichiometry distribution inside the electrode within commercially standard battery geometry, e.g., coin cells with stainless steel casings. Here, we map the distribution of Li+ chemical stoichiometry in the electrode microstructure inside a working coin cell battery to show the amount of electrode materials contributing to energy storage performance using innovative in situ correlative full-field X-ray Compton scattering imaging (XCS-I) and X-ray computed tomography (XCT). We design and fabricate an ultra-thick (∼1 mm) cathode of LiNi0.8Mn0.1Co0.1O2 with a microstructure containing vertically oriented pore arrays using a directional ice templating method. This novel technique paves a new way to map low atomic number elements in 3D structures and study how the microstructure improves Li+ ion diffusivity and energy storage performance.
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Dec 2022
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I15-1-X-ray Pair Distribution Function (XPDF)
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Zhimin
Chen
,
Tao
Du
,
Søren S.
Sørensen
,
Rasmus
Christensen
,
Qi
Zhang
,
Lars R.
Jensen
,
Oxana
Magdysyuk
,
Maria
Diaz-Lopez
,
Mathieu
Bauchy
,
Yuanzheng
Yue
,
Morten M.
Smedskjaer
Diamond Proposal Number(s):
[30401]
Open Access
Abstract: Glass materials are potential candidates as solid electrolytes for batteries, but the atomistic origins of the variations in their properties and functionalities with composition are not well understood. Here, based on combined experimental and simulation techniques, we investigate the structural origin of the variation in fracture toughness and ionic conductivity of lithium borophosphate glass electrolytes with varying compositions. We focus on these properties since they are critically important for mechanical stability and electrochemical performances of glassy electrolytes. To this end, we have performed molecular dynamics simulations combined with X-ray total scattering experiments to provide the atomic picture of the disordered structure of borophosphate glass. The mechanical properties have been characterized through single-edge precracked beam measurements and axial tensile simulations. We find that the deformation and fracture behaviors of the electrolytes are governed by bond switching events of boron, which dissipate the strain energy during fracture. The migration of lithium ions in the electrolyte network is facilitated by hopping between superstructural rings, which reflects the important role of medium-range order structure in determining the lithium-ion diffusion. These findings have important implications for the design of future glassy electrolytes.
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Nov 2022
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I12-JEEP: Joint Engineering, Environmental and Processing
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Alexis
Cartwright-Taylor
,
Maria-Daphne
Mangriotis
,
Ian G.
Main
,
Ian B.
Butler
,
Florian
Fusseis
,
Martin
Ling
,
Edward
Andò
,
Andrew
Curtis
,
Andrew F.
Bell
,
Alyssa
Crippen
,
Roberto E.
Rizzo
,
Sina
Marti
,
Derek D. V.
Leung
,
Oxana V.
Magdysyuk
Diamond Proposal Number(s):
[22517]
Open Access
Abstract: Catastrophic failure in brittle, porous materials initiates when smaller-scale fractures localise along an emergent fault zone in a transition from stable crack growth to dynamic rupture. Due to the rapid nature of this critical transition, the precise micro-mechanisms involved are poorly understood and difficult to image directly. Here, we observe these micro-mechanisms directly by controlling the microcracking rate to slow down the transition in a unique rock deformation experiment that combines acoustic monitoring (sound) with contemporaneous in-situ x-ray imaging (vision) of the microstructure. We find seismic amplitude is not always correlated with local imaged strain; large local strain often occurs with small acoustic emissions, and vice versa. Local strain is predominantly aseismic, explained in part by grain/crack rotation along an emergent shear zone, and the shear fracture energy calculated from local dilation and shear strain on the fault is half of that inferred from the bulk deformation.
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Oct 2022
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Abstract: Manufacturing austenitic stainless steels (ASSs) using additive manufacturing is of great interest for cryogenic applications. Here, the mechanical and microstructural responses of a 316L ASS built by laser powder bed fusion were revealed by performing in situ neutron diffraction tensile tests at the low-temperature range (from 373 to 10 K). The stacking fault energy almost linearly decreased from 29.2 ± 3.1 mJm−2 at 373 K to 7.5 ± 1.7 mJm−2 at 10 K, with a slope of 0.06 mJm−2K−1, leading to the transition of the dominant deformation mechanism from strain-induced twinning to martensite formation. As a result, excellent combinations of strength and ductility were achieved at the low-temperature range.
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Sep 2022
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I12-JEEP: Joint Engineering, Environmental and Processing
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Diamond Proposal Number(s):
[22992]
Open Access
Abstract: Purpose: Freshwater is an increasingly scarce natural resource, essential for agricultural production. As plants consume 70% of the world’s freshwater, a reduction in their water use would greatly reduce global water scarcity. Plants with improved Water Use Efficiency (WUE) such as those with altered expression of the Epidermal Patterning Factor (EPF) family of genes regulating stomatal density, could help reduce plant water footprint. Little however, is known about how this modification in Arabidopsis thaliana. L. affects root architectural development in soil, thus we aim to improve our understanding of root growth when stomatal density is altered. Methods: We used X-Ray synchrotron and neutron imaging to measure in three dimensions, the root system architecture (RSA) of Arabidopsis thaliana. L. plants of three different genotypes, namely that of the wild type Columbia (Col 0) and two different EPF mutants, EPF2OE and epf2-1 (which show reduced and increased stomatal density, respectively). We also used the total biomass and carbon isotope discrimination (Δ) methods to determine how WUE varies in these genotypes when grown in a sandy loam soil under controlled conditions. Results: Our results confirm that the EPF2OE line had superior WUE as compared to the wild type using both the Δ and total biomass method. The epf2-1 mutant, on the other hand, had significantly reduced WUE using the Δ but not with the biomass method. In terms of root growth, the RSAs of the different genotypes had no significant difference between each other. There was also no significant difference in rhizosphere porosity around their roots as compared to bulk soil for all genotypes. Conclusion: Our results indicate that the EPF mutation altering stomatal density in Arabidopsis thaliana. L. plants did not have an adverse effect on root characteristics thus their wide adoption to reduce the global freshwater footprint is unlikely to compromise their soil foraging ability.
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Aug 2022
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