I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[30280]
Open Access
Abstract: Crystalline solvates, including hydrates, hold untapped potential in pharmaceutical development, yet their exploitation remains minimal due to the difficult and laborious task of unequivocally establishing their physical stabilities. We introduce Controlled Solvent-Activity Liquid-Assisted Grinding (CSA-LAG), a mechanochemical protocol that offers solvate phase boundary elucidation by varying the activity of a chosen solvent in defined binary/ternary mixtures and analysing the equilibrated resulting solid form. Using small API amounts, CSA-LAG reaches equilibrium within minutes and yields critical solvent activities that delimit neat, hydrated, solvated and competing-solvate domains. The method uses mixtures of known thermodynamic activities, requires far less material and time than traditional slurries and affords high reproducibility. Applied to four pharmaceutical compounds, CSA-LAG reproduces slurry boundaries and quantifies activity thresholds for single, stepwise and competitive solvations. Defining these boundaries enables rational form selection and process design either by avoiding or targeting solvates, whilst turning a month-scale empirical screening into a rapid, thermodynamically guided workflow.
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Jan 2026
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B18-Core EXAFS
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Run
Ran
,
Haoliang
Huang
,
Qingqing
Chen
,
Fei
Lin
,
Zhipeng
Yu
,
Weifeng
Su
,
Chenyue
Zhang
,
Qingsen
Jia
,
Jingwei
Wang
,
Yang
Zhao
,
Kaiyang
Xu
,
Binwen
Zeng
,
Yaowen
Xu
,
Weimian
Zhang
,
Zhijian
Peng
,
Lifeng
Liu
Diamond Proposal Number(s):
[36104]
Abstract: Sulfur quantum dots (SQDs) represent an emerging class of metal-free, biocompatible luminescent nanomaterials, yet their synthesis remains challenged by harsh conditions, high energy consumption, and limited scalability. Herein, we report a highly value-added strategy coupling SQD synthesis with hydrogen production through sulfion (S2−) oxidation reaction (SOR) assisted alkaline-modified seawater electrolysis (SWE). Such coupling substantially lowers the energy demand for electrolysis and effectively circumvents the interfering chlorine evolution at the anode. An efficient and stable cobalt single-atom catalyst (Co-SAs-PNC) is developed to boost SOR, achieving a large current density of 500 mA cm−2 at 0.536 V vs. reversible hydrogen electrode in alkaline-modified natural seawater and operating stably for 116 h. A flow cell comprising Co-SAs-PNC as the anode catalyst and commercial Pt/C as the cathode catalyst requires only 1.01 V to reach 500 mA cm−2 and shows outstanding durability of >450 h. Besides valuable hydrogen generated at the cathode, the polysulfides electrochemically derived at the anode can be readily converted to multicolor photoluminescent SQDs. Comprehensive in situ/operando experiments and theoretical calculations elucidate the SOR mechanism at isolated Co sites. This work not only opens a new avenue for sustainable SQD production but also remarkably enhances the economic viability of the SWE technology.
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Jan 2026
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B18-Core EXAFS
I18-Microfocus Spectroscopy
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Swaroop
Chakraborty
,
Iuliia
Mikulska
,
Pankti
Dhumal
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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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Diamond Proposal Number(s):
[33430]
Open Access
Abstract: The electrochemical reduction of N2 in aqueous media and ambient conditions would present a great advancement in the defossilization of the fertilizer and energy sector, if the obstacles to this technology were not as significant as they are at present. Some recent reports have raised doubts about whether the electrochemical nitrogen reduction reaction (eNRR) is even possible in aqueous media. Herein, a type of metal-organic framework (MOF)-derived Fe and Zn single atom catalyst for the eNRR is revisited, which has been reported more than once in recent literature to be active for eNRR in aqueous media. Electrochemical measurements reported here show the inactivity of the investigated iron-based catalysts for the eNRR in neutral aqueous media when contaminations are excluded. In stark contrast, the reduction of NOx contamination to ammonia is shown to be a possible reason for false positive results. The reduction of nitrate to ammonia (NO3-RR) is itself an emerging field of research that investigates the conversion of nitrate from wastewater to ammonia. For the NO3-RR, the MOF-derived catalysts show good activity and selectivity, which depends on the iron site density in the catalyst. An ammonia yield of 19.1 mg h−1 mgcat−1 at −1.0 V versus RHE and a maximum faradaic efficiency (FE) of 100% at −0.9 V versus RHE is achieved.
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Dec 2025
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Open Access
Abstract: Slow pyrolysis of fructose-derived hydrothermal carbon spheres at temperatures between 200 °C to 600 °C has been investigated using X-ray Raman spectroscopy and pyrolysis gas chromatography-mass spectrometry in combination with infrared spectroscopy, elemental analysis and thermogravimetry. This study demonstrates the application of temperature resolved X-ray Raman spectroscopy to map the evolution of carbon functionality in complex organic materials. The results show that thermolysis of the polyfuranic linking units within hydrothermal carbon occurs between 300 °C to 350 °C. At pyrolysis temperatures above 350 °C, a stable C-O species is observed. The combination of X-ray Raman and pyrolysis GCMS is used in a synergistic approach to monitor both evolving pyrolysate chemistry and bulk carbon composition. The evolution of key furanic and aromatic analytes during pyrolysis is reported. This work contributes to our understanding of the thermal stability and reactivity of these materials, which is essential for optimizing their applications as catalyst supports.
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Dec 2025
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B21-High Throughput SAXS
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Diamond Proposal Number(s):
[35585]
Open Access
Abstract: The self-assembly in aqueous solution and conformation of lipopeptides C16-WKK, C16-KWK, C16-YKK and C16-KYK is compared and examined. Remarkable differences are observed among the systems despite the small sequence changes comparing C16-XKK with the C16-KXK homologue (X = W or Y), depending on pH. These are rationalized using a molecular theory for amphiphile self-assembly (MOLT) to predict the morphology along with atomistic molecular dynamics simulations to probe local conformation and packing, along with new experimental data from small-angle X-ray scattering (SAXS) and FTIR spectroscopy. MOLT correctly describes the high-pH morphology behavior, i.e., fibrils for C16-XKK, and lamellar nanotapes for C16-KXK, although it predicts micelles for all systems at low pH, whereas experiments indicate that this only occurs for the C16-XKK lipopeptides, not the C16-KXK, which form lamellar nanotapes stable over an extended range of pH 2–12. Atomistic MD reveals β-sheet conformation is more favored for the C16-XKK lipopeptides which also have enhanced aggregation propensity compared to C16-KXK analogues. The extent of π-stacking was higher for the latter lamellar nanotape structures. The extent of hydrogen bonding is higher for the tyrosine-containing molecules than the tryptophan-based ones. The combination of a molecular theory and atomistic MD provides a comprehensive insight into the remarkable sequence- and pH-dependent molecular ordering within these model lipopeptides which will enable the rational design of future peptide amphiphiles with targeted nanostructures for desired applications.
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Dec 2025
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I11-High Resolution Powder Diffraction
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Diamond Proposal Number(s):
[36397]
Abstract: The widespread adoption of Li-ion batteries has created a pressing need for effective recycling strategies. A common approach involves producing “black mass”─a mixture of shredded electrode materials─followed by thermal treatment to simplify downstream recovery. Although current collectors (Al and Cu foils) are assumed to be physically separated before pyrolysis, industrial separation is often incomplete, leaving residual foil fragments that can chemically react with cathode materials. Here we investigate the influence of these foils on black mass pyrolysis using simplified model systems composed of pristine LiNi0.8Mn0.1Co0.1O2 and current collector fragments under inert, mildly oxidizing, and reducing atmospheres. Cu foils were found to form lithium copper oxides, LiCuO and Li2CuO2, previously unreported in the Li-ion battery recycling literature. Al foils produced γ-LiAlO2, Li5AlO4, and LiAl2(OH)7·2H2O. The two latter phases readily decompose to γ-LiAlO2, a compound that has been suggested to be detrimental for Li recovery due to its low solubility. We assess the leaching implications of these product phases, with particular attention to γ-LiAlO2, to establish that they readily dissolve in dilute H2SO4/H2O2 solutions, but can reduce Ni and Co leaching efficiency in more realistic black mass mixtures.
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Dec 2025
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[34844, 37870]
Open Access
Abstract: Efficient food resources management, particularly through minimization of waste across the production and supply chain, is essential for creating a resilient, circular agri-food system. The rice industry is one of the largest sectors in agri-food, supporting over half of the global population. This work focuses on valorizing the lipidic fraction of rice bran, a major by-product of rice processing, to contribute to reducing the environmental impact of rice production. Novel purification processes of rice bran wax (RBX) from rice bran are presented, together with their environmental impact assessment. Rice bran butter (RBB) was initially extracted using supercritical CO2, followed by the separation of its main components, rice bran oil (RBO) and rice bran wax (RBX), through combinations of different physical unit operations including crystallization, centrifugation, solvent extraction and filtration. The purification strategies developed involved green solvents such as ethanol and isopropanol, compared to the commonly used hexane. The purified products were characterized in terms of their chemical properties via chromatographic techniques. Differential Scanning Calorimetry (DSC) and X-ray diffraction were used to determine structural and thermal properties of the material extracted. A Life Cycle Assessment (LCA) was also conducted to determine the environmental impact of the designed extraction and separation processes. The LCA highlighted that the optimal process configuration balances wax extraction yield, energy consumption, and solvent use. Process #2 using ethanol emerged as the most sustainable option, achieving the highest performance with the lowest environmental impact.
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Dec 2025
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I04-Macromolecular Crystallography
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J. Henry
Blackwell
,
Simon C. C.
Lucas
,
Giovanni
Battocchio
,
Ulf
Börjesson
,
Mark J.
Bostock
,
Erin L.
Braybrooke
,
Tony
Cheung
,
Matthew A.
Cottee
,
Kevin C.
Beaumont
,
Andrea
Gohlke
,
David
Hargreaves
,
Maaike
Van Hoek- Emmelot
,
Vera
Van Hoeven
,
Chimed
Jansen
,
Aarti
Kawatkar
,
Olaf
Kinzel
,
Praveen
Kumar
,
Lea
Kupcova
,
Michael D.
Lainchbury
,
Leonardo
Leon
,
Alexander G.
Milbradt
,
Adeline
Palisse
,
Markus
Schade
,
Kim
Van Rijbroek
,
Claudia
Sacchetto
,
Rick
Schellekens
,
Nancy
Su
,
Hua
Xu
,
Heng
Zhao
,
Yunhua
Chen
,
Shen
Huang
Diamond Proposal Number(s):
[20015]
Abstract: We describe herein the discovery and optimization of a potent and irreversible cellular probe for selective labeling of Bfl-1, a member of the Bcl-2 family. This chemical series demonstrates robust selectivity for Bfl-1 over other related antiapoptotic proteins and exhibits favorable cellular potency as well as promising in vivo pharmacokinetics. Notably, compound 25 achieves a kinact/KI value of 9300 M–1s–1 and elicits caspase activation at submicromolar concentrations in cellular assays. To comprehensively profile proteome-wide selectivity, we performed chemoproteomic analyses on compound 25 alongside our previously reported Bfl-1 inhibitors. This enabled critical insights into potential off-target interactions and facilitated direct comparison of off-target profiles among distinct chemotypes targeting Bfl-1.
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Dec 2025
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B18-Core EXAFS
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Diamond Proposal Number(s):
[38116]
Open Access
Abstract: Increasing use of lithium-ion batteries (LIBs) urges for efficient recycling strategies for their components. Direct recycling methods for cathode materials, based on repairing the structure of the degraded cathode particles without destroying the bulk phase, are promising energy-saving alternatives to traditional metallurgy processes that involve several steps and use large volumes of chemicals causing secondary pollution. Herein, we report a novel and scalable method for the direct electrochemical recycling of spent lithium iron phosphate (LFP) powder in a flow cell via redox mediation. In this method, pellets of spent LFP powder (S-LFP) placed in a tank are directly reduced and relithiated by a redox mediator dissolved in a Li-containing aqueous electrolyte, pumped from an electrochemical cell stack to the relithiation tank. Redox mediators transport charge to the S-LFP pellets from the electrochemical cell, where Li4Fe(CN)6 is oxidized and Li ions are supplied from a Li4Fe(CN)6-containing counter compartment through an ion-selective membrane. The consumption of the regenerating redox mediator solution is minimal via a closed-loop electrochemical regeneration reaction. Successful S-LFP regeneration using two redox mediators, with different energy demand processes, is confirmed by structural and electrochemical characterization.
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Dec 2025
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