B21-High Throughput SAXS
labSAXS-Offline SAXS and Sample Environment Development
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Abshar
Hasan
,
Andrey
Chuvilin
,
Alexander
Van Teijlingen
,
Helena
Rouco
,
Christopher
Parmenter
,
Federica
Venturi
,
Michael
Fay
,
Gabriele
Greco
,
Nicola M.
Pugno
,
Jan
Ruben
,
Charlotte J. C.
Edwards-Gayle
,
Benjamin
Myers
,
Ingrid
Dreveny
,
Nathan
Cowieson
,
Adam
Winter
,
Sara
Gamea
,
X. Frank
Walboomers
,
Tanvir
Hussain
,
José Carlos
Rodríguez-Cabello
,
Frankie
Rawson
,
Tell
Tuttle
,
Sherif
Elsharkawy
,
Avijit
Banerjee
,
Stefan
Habelitz
,
Alvaro
Mata
Diamond Proposal Number(s):
[32387]
Open Access
Abstract: Tooth enamel is characterised by an intricate hierarchical organization of apatite nanocrystals that bestows high stiffness, hardness, and fracture toughness. However, enamel does not possess the ability to regenerate, and achieving the artificial restoration of its microstructure and mechanical properties in clinical settings has proven challenging. To tackle this issue, we engineer a tuneable and resilient supramolecular matrix based on elastin-like recombinamers (ELRs) that imitates the structure and function of the enamel-developing matrix. When applied as a coating on the surface of teeth exhibiting different levels of erosion, the matrix is stable and can trigger epitaxial growth of apatite nanocrystals, recreating the microarchitecture of the different anatomical regions of enamel and restoring the mechanical properties. The study demonstrates the translational potential of our mineralising technology for treating loss of enamel in clinical settings such as the treatment of enamel erosion and dental hypersensitivity.
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Nov 2025
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B21-High Throughput SAXS
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Diamond Proposal Number(s):
[28884, 32784]
Open Access
Abstract: Molecular solar thermal energy storage (MOST) materials are a promising method for renewable energy storage that captures solar energy and releases it on demand as heat. Azobenzene is attractive for MOST applications due to its photoreversible E–Z isomerization. Recently, phase-change materials have been formed using azobenzene to increase their energy-storage capacity; however, these condensed phases often lower the isomerization degree, which is only recovered on dissolution. In this work, sparing solvent addition is used to drive the self-assembly of azobenzene photosurfactants (AzoPS) into lyotropic liquid crystal (LLC) phases, which are explored for MOST applications for the first time. Using small-angle X-ray scattering (SAXS), polarized optical microscopy, and differential scanning calorimetry (DSC), we show that the structure-isomerization behavior, and energy-storage properties of these light-responsive LLCs can be systematically tuned by adjusting the photosurfactant structure, solvent, and concentration. Furthermore, by developing a method that combines SAXS with in situ DSC, we directly correlate the isomerization-induced LLC phase transitions to their energy-storage contributions. The formation of LLC phases through solvent addition both enhances the degree of isomerization (by up to 20%) and amplifies the structural disordering on isomerization, resulting in energy-storage densities of up to 123 J g–1. The ability to tune both the structure and isomerization properties in LLC materials suggests significant promise for MOST applications. In addition, the combination of advanced characterization methods used to establish the structure–isomerization–enthalpy (LLC-photoswitch-phase change) relationships provides unique insight into these multicomponent systems and accelerates the design pathways to future iterations for competitive solar energy storage devices.
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Aug 2025
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B21-High Throughput SAXS
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Diamond Proposal Number(s):
[28976]
Abstract: Structural characterization of commercially available gluten-free pasta is achieved here by combining small-angle x-ray and neutron scattering with contrast variation, and compared to the analogous regular gluten-containing pasta variety. In particular, the use of neutron and contrast variation allowed us to isolate the information about the gluten matrix and the starch granules. The broad peak that reflects the structure of the starches is lost as a function of cooking. This effect is more dramatic for the gluten-free pasta, indicating that the absence of gluten strongly promotes the gelation of the starches. Furthermore, the presence of salt in the cooking water is found to preserve the structural properties of the pasta, while at the same time it promotes the degradation of the starch granules. This study is the first step for a structural characterization of commercially-available pasta, moving forward the classic model system used so far to achieve information on the relation between pasta microstructure and its digestibility.
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Aug 2025
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B21-High Throughput SAXS
I03-Macromolecular Crystallography
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Muhammad
Saleem
,
Chan
Li
,
Bubacarr G.
Kaira
,
Alexander K.
Brown
,
Monika
Pathak
,
Shabir
Najmudin
,
Nathan
Cowieson
,
Ingrid
Dreveny
,
Clare
Wilson
,
Aleksandr
Shamanaev
,
David
Gailani
,
Stephanie A.
Smith
,
James H.
Morrissey
,
Helen
Philippou
,
Jonas
Emsley
Diamond Proposal Number(s):
[37038]
Open Access
Abstract: Factor XIIa (FXIIa) is generated from its zymogen factor XII (FXII) by contact with polyanions such as inorganic polyphosphates. FXIIa cleaves the substrates prekallikrein and factor XI, triggering inflammatory cascades and plasma coagulation. From the N-terminus, FXII has fibronectin type II (FnII), epidermal growth factor-1 (EGF1), fibronectin type I (FnI), EGF2 and kringle domains. The N-terminal domains of FXII mediate polyanion and Zn2+ binding. To understand how ligand binding to polyanions and Zn2+ is coordinated across multiple domains, we determined the crystal structure of recombinant FXII domains 1–5 (FXIIHC5) to 3.4 Å resolution. A separate crystal structure of the isolated FXII FnII domain at 1.2 Å resolution revealed two bound Zn2+ ions. In FXIIHC5 a head-to-tail interaction is formed between the FnII and kringle domains, co-localizing the lysine-binding sites of the kringle domain and the cation-binding site of the FnII domain. Two FXIIHC5 monomers interlock, burying a large surface area of 2067 Å2, such that two kringle domains point outwards separated by a distance of 20 Å. The polyanion-binding site in the EGF1 domain is localized onto a plane together with the FnII and FnI domains. Using native mass spectrometry, we detected a major FXIIHC5 monomer peak and a minor dimer peak. Small-angle X-ray scattering and gel-filtration chromatography revealed the presence of monomers and dimers in solution. These FXII N-terminal domain structures provide a holistic framework to understand how the mosaic domain structure of FXII assembles diverse ligand-binding sites in three dimensions.
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Jul 2025
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B21-High Throughput SAXS
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Diamond Proposal Number(s):
[23942]
Open Access
Abstract: Performance plastics, such as poly(methyl methacrylate), underpin the modern economy. Global manufacturing of plastic precursors relies on fossil carbon sources, and the urgently needed shift toward renewable carbon use through biofermentation is hindered by the low tolerance of producer strains to methacrylate esters. The principal mode of butyl methacrylate cellular toxicity is membrane disruption. To understand this process, the conditions for membrane stability, and recovery after solvent shock, we investigate the phase stability of hydrated lipid membranes at high levels of a key intermediate, butyl methacrylate. We assess the role of cis- vs trans-unsaturation in 18-carbon chain phospholipids on butyl methacrylate-induced phase conversion and polymorphism. Using ssNMR, SAXS and cryoEM, we demonstrate the formation of stable lipidic cubic phases in hydrated lipid/solvent (cis-chain phospholipid lipid/butyl methacrylate) systems at a 1:6 molar ratio entirely lacking monoolein. Transient lipidic cubic phases form in trans-chain phospholipid/butyl methacrylate systems, which slowly convert to bilayers through a spontaneous “membrane healing” process during recovery after solvent shock. The observed bicontinuous nanostructures with a cubic phase architecture coexist with a stable, monocontinuous hydrated phase of the same morphology but with simpler topological connectivity, which demonstrates that phase stability in cubic phases does not require topological complementarity. We propose trans-lipid substitutions in membranes of fermentative strains as a key step toward sustainable production of methacrylate esters.
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Jul 2025
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B21-High Throughput SAXS
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Diamond Proposal Number(s):
[30763]
Open Access
Abstract: Metal nanocrystals (M-NCs) and their supramolecular assemblies have attracted significant interest from the scientific community due to their wide range of applications arising from the possibility of accurately tuning the M-NCs properties through self-assembly into supramolecular aggregates. In this study, we investigate the complex interplay between capping agent surface coverage and solvent-capping agent interactions in the self-assembly process of M-NCs into supramolecular structures. Specifically, we explore the self-assembly behavior of gold (Au-NCs), silver (Ag-NCs), and platinum (Pt-NCs) nanocrystals upon functionalization with oleic acid (OA) in water using a microemulsion approach. Through a multi-technique analysis, we demonstrate the critical role of ligand density and solvent choice in driving the formation of highly ordered supramolecular structures. By increasing the surface coverage of the M-NC ligands, we observed a transition to more organised assemblies, with the interaction between the oleylamine alkyl chain and the functionalization medium further modulating the type of supramolecular arrangement. Moreover, we highlight the profound influence of both the external environment and supramolecular aggregation on the optical properties of the M-NCs. This work provides crucial insights into the factors that govern nanocrystals’ self-assembly and optical behavior, with broad implications for the design and application of nanomaterials in nanotechnology and materials science.
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Jun 2025
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B21-High Throughput SAXS
labSAXS-Offline SAXS and Sample Environment Development
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Diamond Proposal Number(s):
[34342, 40687]
Open Access
Abstract: Semaglutide is a lipopeptide with important applications in the treatment of diabetes, obesity, and other conditions. This class of drug (glucagon-like peptide-1 agonists and other lipidated peptides) may be susceptible to aggregation due to the tendency of lipopeptides to self-assemble into various nanostructures. Here, we show using cryogenic-TEM, small-angle X-ray scattering, and molecular dynamics simulations that semaglutide in aqueous solution undergoes slow aggregation into spherical micelles in water at sufficiently high concentration. A small population of needle-shaped fibril aggregates is also observed. At a lower concentration, dimer and trimer structures are formed. The micelles, once formed, are stable toward further aging. The aggregation influences the effect of semaglutide on the permeability of an epithelial gut model membrane of Caco-2 cells. These findings are expected to be important in understanding the long-term stability of semaglutide solutions and the potential effects of aggregation on therapeutic efficacy.
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May 2025
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B21-High Throughput SAXS
I03-Macromolecular Crystallography
I04-1-Macromolecular Crystallography (fixed wavelength)
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Diamond Proposal Number(s):
[9306, 12346, 15613]
Open Access
Abstract: Dynamic ADP-ribosylation signalling is a crucial pathway that controls fundamental cellular processes, in particular, the response to cellular stresses such as DNA damage, reactive oxygen species and infection. In some pathogenic microbes the response to oxidative stress is controlled by a SirTM/zinc-containing macrodomain (Zn-Macro) pair responsible for establishment and removal of the modification, respectively. Targeting this defence mechanism against the host’s innate immune response may lead to novel approaches to support the fight against emerging antimicrobial resistance. Earlier studies suggested that Zn-Macros play a key role in the activation of this defence. Therefore, we used phylogenetic, biochemical, and structural approaches to elucidate the functional properties of these enzymes. Using the substrate mimetic asparagine-ADP-ribose as well as the ADP-ribose product, we characterise the catalytic role of the zinc ion in the removal of the ADP-ribosyl modification. Furthermore, we determined structural properties that contribute to substrate selectivity within the different Zn-Macro branches. Together, our data not only give new insights into the Zn-Macro family but also highlight their distinct features that may be exploited for the development of future therapies.
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Sep 2024
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B21-High Throughput SAXS
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Diamond Proposal Number(s):
[28884]
Open Access
Abstract: Dynamic, responsive materials can be built using photosurfactants (PS) that self-assemble into ordered nanostructures, such as micelles or liquid crystals. These PS contain photoswitchable groups, such as azobenzene (Azo) or, more recently, arylazopyrazoles (AAPs), which change shape and polarity on photoisomerisation between the E and Z states, thus changing the self-assembled structure. Small-angle X-ray scattering (SAXS) is a powerful technique to probe the morphology of PS and can be used to measure the mechanisms of structural changes using in-situ light irradiation with rapid, time-resolved data collection. However, X-ray irradiation has been shown previously to induce Z-to-E isomerisation of Azo-PS, which can lead to inaccuracies in the measured photostationary state. Here, we investigate the effect of light and X-ray irradiation on micelles formed from two different PS, containing either an Azo or AAP photoswitch using SAXS with in-situ light irradiation. The effect of X-ray irradiation on the Z isomer is shown to depend on the photoswitch, solvent, concentration and morphology. We use this to create guidelines for future X-ray experiments using photoswitchable molecules, which can aid more accurate understanding of these materials for application in solar energy storage, catalysis or controlled drug delivery.
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Aug 2024
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B21-High Throughput SAXS
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Beatrice E.
Jones
,
Ann
Fitzpatrick
,
Kieran
Fowell
,
Charlotte J. C.
Edwards-Gayle
,
Nikul
Khunti
,
Katsuaki
Inoue
,
Steven
Daniels
,
Eugene
Williams
,
Camille
Blayo
,
Rachel C.
Evans
,
Nathan
Cowieson
Open Access
Abstract: Beamline B21 at the Diamond Light Source synchrotron in the UK is a small-angle X-ray scattering (SAXS) beamline that specializes in high-throughput measurements via automated sample delivery systems. A system has been developed whereby a sample can be illuminated by a focused beam of light coincident with the X-ray beam. The system is compatible with the highly automated sample delivery system at the beamline and allows a beamline user to select a light source from a broad range of wavelengths across the UV and visible spectrum and to control the timing and duration of the light pulse with respect to the X-ray exposure of the SAXS measurement. The intensity of the light source has been characterized across the wavelength range enabling experiments where a quantitative measure of dose is important. Finally, the utility of the system is demonstrated via measurement of several light-responsive samples.
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Jul 2024
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