B18-Core EXAFS
I18-Microfocus Spectroscopy
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Swaroop
Chakraborty
,
Iuliia
Mikulska
,
Pankti
Dhumal
,
Nathan
Langford
,
Susan
Nehzati
,
Rhiannon
Boseley
,
Sang
Pham
,
Christian
Pfrang
,
Manpreet
Kaur
,
Eugenia
Valsami-Jones
,
Konstantin
Ignatyev
,
Dhruv
Menon
,
Superb K.
Misra
,
Iseult
Lynch
Diamond Proposal Number(s):
[33674, 35117, 35776, 40080, 40942]
Open Access
Abstract: Metal–organic frameworks (MOFs) hold immense potential for applications from separations to catalysis, yet their long-term behavior across real-world environments remains unclear. Here we introduce a hierarchical exposure framework that tracks the structural and chemical transformations in the archetypal zirconium MOF UiO-66 across sequential compartments─atmospheric gases, air, aqueous media and a biological host─and resolves how prior exposures condition or prime subsequent transformations. Using synchrotron-based spectroscopy, we find that oxidative/reactive gases leave the Zr-carboxylate nodes essentially intact, whereas exposure to environmentally relevant aqueous media initiates partial shifts in local Zr coordination and introduces oxygen into the pores─with transformation extent governed by the chemistry of the environmental matrices. Strikingly, acute exposure (24 h) to the water flea Daphnia magna drives profound framework degradation and respeciation to Zr hydroxide species. Microfocus XRF maps show that Zr is highly localized in the animal’s digestive tract, and region-specific XANES confirms uniform speciation across its tissues. Our findings establish a paradigm shifting cross-compartment transformation hierarchy in which biological processes can dominate the fate of stable MOFs even when abiotic exposures appear benign. Thus, organism-level biotransformation should be performed as a necessary part of environmental safety assessments and materials design.
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Jan 2026
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E02-JEM ARM 300CF
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Woo Hyeon
Jeong
,
Junzhi
Ye
,
Jongbeom
Kim
,
Rui
Xu
,
Xinyu
Shen
,
Chia-Yu
Chang
,
Eilidh L.
Quinn
,
Hyungju
Ahn
,
Myoung Hoon
Song
,
Peter D.
Nellist
,
Henry J.
Snaith
,
Yunwei
Zhang
,
Bo Ram
Lee
,
Robert L. Z.
Hoye
Diamond Proposal Number(s):
[40059]
Open Access
Abstract: The anisotropy of perovskite nanoplatelets (PeNPLs) opens up many opportunities in optoelectronics, including enabling the emission of linearly polarized light. But the limited stability of PeNPLs is a pressing challenge, especially for red-emitting CsPbI3. Herein, we address this limitation by alloying formamidinium (FA) into the perovskite cuboctahedral site. Unlike Cs/FA alloying in bulk thin films or nanocubes, FA incorporation in nanoplatelets requires meticulous control over the reaction conditions, given that nanoplatelets are obtained in kinetically-driven growth regimes instead of thermodynamically-driven conditions. Through in-situ photoluminescence (PL) measurements, we find that excess FA leads to uncontrolled growth, where phase impurities and nanoplatelets of multiple thicknesses co-exist. Restricting the FA content to up to 25% Cs substitution enables monodisperse PeNPLs, and increases the PL quantum yield (from 53% to 61%), exciton lifetime (from 18 ns to 27 ns), and stability in ambient air (from ~2 days to >7 days) compared to CsPbI3. This arises due to hydrogen bonding between FA and the oleate and oleylammonium ligands, anchoring them to the surface to improve optoelectronic properties and stability. The reduction in non-radiative recombination, improvement in the nanoplatelet aspect ratio, and higher ligand density lead to FA-containing PeNPLs more effectively forming edge-up superlattices, enhancing the PL degree of linear polarization from 5.1% (CsPbI3) to 9.4% (Cs0.75FA0.25PbI3). These fundamental insights show how the stability limitations of PeNPLs could be addressed, and these materials grown more precisely to improve their performance as polarized light emitters, critical for utilizing them in next-generation display, bioimaging, and communications applications.
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Jan 2026
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B18-Core EXAFS
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Diamond Proposal Number(s):
[37736]
Open Access
Abstract: 99Tc is a long-lived radioactive fission product whose subsurface mobility is governed by redox conditions. Under oxic conditions, soluble Tc(VII)O4– is mobile, whereas under reducing conditions, poorly soluble Tc(IV) phases limit transport. Microcosm studies have frequently reported TcO2-like solids and, less consistently, Tc(IV)-sulfides. The stability of Tc(IV)-sulfides under environmentally relevant conditions remains unclear. Here, we used flowing sediment columns representative of the Sellafield subsurface to examine Tc speciation and stability over ∼1 year. Under reducing conditions, >90% of added TcO4– (400 μg) was retained under both Fe(III)- and sulfate-reducing conditions. X-ray absorption spectroscopy showed TcO2-like phases dominated in Fe(III)-reducing columns, while Tc(IV)-sulfides dominated after sustained sulfate reduction. Sequential extractions indicated that Tc in sulfidic sediments was more recalcitrant (≤23% released by weak acids) than in Fe(III)-reducing systems (∼60% released). With oxic groundwater pumping, effluent Tc sourced from the sediments rose rapidly. Over 160 days, the sulfidic columns remobilized ∼25% of their Tc inventory compared to ∼50% in Fe(III)-reducing columns. The Tc(IV)-sulfides also gradually oxidized to form TcO2 phases. While Tc(IV)-sulfides may enhance Tc retention under reducing conditions, TcO2 phases more likely govern 99Tc mobility during long-term redox cycling. Our findings provide new constraints for modeling Tc fate at contaminated sites and in radioactive waste disposal.
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Dec 2025
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B07-B1-Versatile Soft X-ray beamline: High Throughput ES1
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Diamond Proposal Number(s):
[34919, 37955]
Open Access
Abstract: A combination of experimental methods and computational techniques have been used to investigate the composition of the zinc ferrite (ZnFe2O4) (1 1 1) single crystal surface under different preparation methods. Surface-sensitive XPS and NEXAFS measurements show that upon annealing in ultra-high vacuum (UHV), Zn depletion occurs, leading to the formation of an iron-rich (1 1 1) surface, whereas annealing in the presence of O2 gas maintains a more bulk-like ZnFe2O4 surface composition. Analysis of the Fe 2p photoemission (XPS) and Fe L edge X-ray absorption signals shows a clear difference in iron oxidation state and distribution between the two different preparation conditions. After annealing in UHV, a mixed Fe2+/Fe3+ oxidation state and a cation distribution like that of a magnetite (Fe3O4) structure is observed, whereas after annealing in oxygen gas only Fe3+, mostly in octahedral coordination, is observed, as expected for a ZnFe2O4 structure. Temperature-dependent XPS confirms significant Zn depletion in the near-surface region above 500 °C under UHV, with almost no Zn remaining at 600 °C; under an O2 atmosphere no zinc depletion is observed up to 600 °C. A theoretical model based on DFT simulations illustrates how reduction from ZnFe2O4 to Fe3O4 with formation of O2 and Zn gas is thermodynamically feasible under UHV conditions, whereas the same reaction is not favourable at higher oxygen partial pressures. Our findings demonstrate the strong impact that UHV treatment has on zinc ferrite surfaces, and cautions that UHV environments, routinely employed for surface analysis, can themselves induce substantial modifications to the surface, thereby complicating the interpretation of measurements in the context of catalytically relevant conditions.
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Dec 2025
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Aquilos-CryoFIB at Diamond
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Diamond Proposal Number(s):
[31336]
Open Access
Abstract: Regulation of Lamin A/C levels and distribution is crucial for nuclear integrity and mechanotransduction via the Linker of Nucleoskeleton and Cytoskeleton (LINC) complex. Dysregulation of Lamin A/C correlates with poor cancer prognosis, and its levels determine sensitivity to the microtubule-stabilising drug paclitaxel. Paclitaxel is well-known for disrupting mitosis, yet it also reduces tumour size in slow-dividing tumours, indicating an additional, poorly characterised interphase mechanism.
Here, we reveal that paclitaxel induces nuclear aberrations in interphase through SUN2-dependent Lamin A/C disruption. Using advanced optical imaging and electron cryo-tomography, we show the formation of aberrant microtubule-vimentin bundles during paclitaxel treatment, which coincides with nuclear deformation and altered Lamin A/C protein levels and organisation at the nuclear envelope. SUN2 is required for Lamin A/C reduction in paclitaxel and is in turn regulated by polyubiquitination. Furthermore, Lamin A/C expression levels determine not only cell survival during treatment but also recovery after drug removal.
Our findings support a model in which paclitaxel acts through both defective mitosis and interphase nuclear-cytoskeletal disruption, providing additional mechanistic insights into a widely used anticancer drug.
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Dec 2025
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I22-Small angle scattering & Diffraction
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M.
Hassan Sk
,
S. M.
Clarke
,
M.
Woolley
,
A.
Osudare
,
S.
Agrawal
,
N.
Sharifi
,
D.
Eberl-Craske
,
R.
Lindsay
,
M. T. L.
Casford
,
A.
Smith
,
N.
Terrill
Diamond Proposal Number(s):
[23699, 28693, 32669]
Open Access
Abstract: In this study we have investigated the nucleation mechanism of ‘sweet’, CO2 corrosion scale in situ using synchrotron scattering under industrially relevant conditions (CO2 saturated brine, ultra-low oxygen (8–32 ppb), 80 °C, pH 6.8, open-circuit-potential (OCP)). Simultaneous small and wide-angle X-Ray Scattering (SAXS-WAXS) measurement allows the phase and state of the nucleating corrosion scale to be characterised as a function of both immersion time and location with respect to the metal/solution interface. The results indicate that a precursor amorphous phase is formed prior to the emergence of a crystalline iron carbonate scale.
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Dec 2025
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I03-Macromolecular Crystallography
I04-1-Macromolecular Crystallography (fixed wavelength)
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Diamond Proposal Number(s):
[30602]
Open Access
Abstract: Fragment-based drug design offers multiple routes to advance from fragments. One approach is to build structure-activity relationships (SAR) from analogue series in direct-to-biology workflows. Analogues can be prepared by automated chemistry and tested as crude reaction mixtures (CRMs) without purification, but assay noise often leads to hit resynthesis, potentially discarding false negatives and reducing SAR dataset size. High-throughput (HT) X-ray crystallography has the potential to address these issues by resolving hits directly from 100s–1000s of CRMs. However, no systematic analytics exist for extracting SAR models from HT crystallographic evaluation of CRMs. Here, we demonstrate that crystallographic SAR (xSAR) can be extracted from CRMs evaluated via HT X-ray crystallography. We developed a simple rule-based ligand scoring scheme that identifies conserved chemical features associated with crystallographic binding and non-binding. Applied to a crystallographic dataset of 957 fragment elaborations in CRMs targeting PHIP(2), a therapeutically relevant bromodomain, our xSAR model demonstrated effectiveness in two proof-of-concept experiments. First, it recovered 26 missed binders in the initial dataset (false negatives), doubling the hit rate and denoising the dataset. Second, it enabled a prospective virtual screen that identified novel hits with informative chemistries and measurable binding affinities. This work establishes a proof-of-concept that xSAR models can be directly extracted from large-scale crystallographic readouts of CRMs, offering a valuable methodology to build SAR models and accelerate design-make-test iterations without requiring CRM hit resynthesis and confirmation. This invites future work to utilise advanced analytics and modelling techniques to further strengthen purification-agnostic workflows.
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Dec 2025
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Open Access
Abstract: Magnetic axial and polar (Dirac) nickel multipoles contribute to resonant X-ray Bragg amplitudes in a symmetry-informed analysis of monoclinic Li2Ni3P4O14 presented for future diffraction experiments. Magnetic long-range order below a temperature of ≃ 14.5 K can be viewed as a two-dimensional trimerized antiferromagnet with Ni ions in two Wyckoff positions in the centrosymmetric (1) magnetic space group P21/c. It permits the coupling to circular polarization in the primary X-ray beam, unlike the corresponding diffraction by an antiferromagnet characterized by anti-inversion (1′) and a linear magnetoelectric effect, e.g. historically significant chromium sesquioxide (Cr2O3) and Cu2(MoO4)(SeO3) [Lovesey & van der Laan (2024View full citation). Phys. Rev. B 110, 174442]. The space group is inferred from neutron Bragg diffraction patterns, without an allowance for permitted Dirac dipoles (anapoles) and quadrupoles [Chikara et al. (2025). Phys. Rev. B 112, 014438].
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Dec 2025
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E02-JEM ARM 300CF
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Xinjuan
Li
,
Zhao
Jiang
,
Si
Chen
,
Yi
Tang
,
Bofeng
Xue
,
Tianhao
Wu
,
Yang
Lu
,
Xavier
Moya
,
Akshay
Rao
,
Zhongzheng
Yu
,
Caterina
Ducati
Diamond Proposal Number(s):
[39081]
Open Access
Abstract: Perovskite quantum dots (PeQDs) offer high photoluminescence quantum efficiencies, precise spectral tunability, and solution-processability, making them promising for advanced optoelectronics. However, their structural and defect evolution under thermal stress remains poorly understood. Here, direct nanoscale insights are provided into temperature-driven phase transition and defect dynamics in CsPbBr3 PeQDs using high-resolution, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images, 4D STEM, and photoluminescence spectroscopy. Sub-ångström imaging at room temperature reveals inherent atomic features and octahedral tilting of the lead halide perovskite lattice in PeQDs, suggesting a pre-tilted, low-symmetry state before thermal perturbation. The cryogenic cooling induces a reversible orthorhombic-to-monoclinic phase transition, distinct from bulk perovskite behavior and accompanied by severe strain localization exceeding 20% at surfaces and grain boundaries. A controlled cryogenic post-synthesis treatment can effectively heal defects and improve radiative recombination, whereas prolonged cryo-treatment introduces irreversible structural degradation. These findings highlight the intrinsic structural flexibility of PeQDs and provide a scalable post-synthesis treatment method to optimize the stability and efficiency of QDs for various optoelectronic applications.
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Dec 2025
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I09-Surface and Interface Structural Analysis
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G.
Cicconi
,
M.
Bosi
,
F.
Mezzadri
,
A.
Ugolotti
,
I.
Cora
,
L.
Seravalli
,
H.
Tornatzky
,
J.
Lähnemann
,
M. R.
Wagner
,
P.
Bhatt
,
P. K.
Thakur
,
T.-L.
Lee
,
A.
Regoutz
,
A.
Baraldi
,
D.
Bersani
,
L.
Cademartiri
,
A.
Parisini
,
B.
Pécz
,
L.
Miglio
,
R.
Fornari
,
P.
Mazzolini
Diamond Proposal Number(s):
[36180]
Open Access
Abstract: The ultra-wide bandgap semiconductor rutile germanium oxide (r-GeO2, Eg ≈ 4.6 eV) is gaining momentum in the quest for novel materials for power electronics. In this work, we experimentally and theoretically investigate the physical mechanisms behind the nucleation and growth of epitaxial (001) r-GeO2 on isostructural r-TiO2 substrates via metalorganic vapor phase epitaxy (MOVPE) using isobutylgermane and O2 precursors. In the identified deposition window, the thin film growth seems to be affected by partial GeO suboxide desorption, and we observe that the layers are always composed of r-GeO2 islands embedded and/or surrounded by amorphous material. Ge/Ti interdiffusion at the epilayer-substrate interface is found at the base of each r-GeO2 island; combining experimental analysis and multiscale theoretical simulations we discuss how such a process is fundamental to achieve partial strain mitigation allowing for the nucleation of epitaxial r-GeO2 and suggest in this regard a limiting threshold to avoid the formation of amorphous material. Moreover, we shed light on the formation of different facets in r-GeO2 at early stages of growth and after merging of islands.
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Dec 2025
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