I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[37889]
Open Access
Abstract: Despite being the most abundant sustainable energy resource, solar energy still faces major challenges in efficient capture and long-term storage. Molecular Solar Thermal Energy Storage (MOST) systems address this issue by employing photoswitchable molecules that absorb sunlight and store energy through reversible isomerization, cyclization or other intramolecular rearrangements. Azobenzenes are attractive due to their well-characterized photoresponsive behavior; however, conventional systems are hindered by low energy density, limited energy storage duration, and a reliance on organic solvents. Here, we present the Micellar Solar Thermal Energy Storage system (MIST) approach based on micellar aggregates that operate effectively across aqueous dispersions and gel states. These systems exhibit progressively enhanced energy storage lifetimes with increasing degrees of self-assembly, while delivering competitive energy densities. The thermal stability arises from restricted molecular mobility within the self-assembled structures and is enhanced on gelation, extending the calculated thermal half-life of the cis isomer from 148 days in dimethyl sulfoxide (DMSO), to 233 days in water, and to 12.8 years in the gel state. Compared to previous azobenzene-based MOST systems, our MIST approach offers significantly extended energy storage durations and improved material processability, including water-compatible formulations and, macroscopic heat release in the gel state (up to 5.7 °C).
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Nov 2025
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I22-Small angle scattering & Diffraction
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Open Access
Abstract: Carbon materials are essential for emerging energy applications and there is a pressing need to be able to produce carbons with controlled properties from sustainable precursors. Iron-catalysed graphitization of biomass is an attractive approach, where simple iron salts are used to convert organic matter to graphitic carbons at relatively low temperature. The choice of iron salt can have a significant impact on the chemical and structural properties of carbons derived from biomass. In this paper, we report a detailed mechanistic investigation of iron catalysed graphitization of cellulose by Fe(NO3)3 and FeCl3. In situ small and wide angle X-ray scattering and electron microscopy show that the evolution of catalyst particles from the two salts follows very different pathways. Remarkably, graphitization by FeCl3 is an order of magnitude faster than by Fe(NO3)3.
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Jul 2025
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B21-High Throughput SAXS
I22-Small angle scattering & Diffraction
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Simona
Bianco
,
Ravi R.
Sonani
,
Dipankar
Ghosh
,
Tejaswini
Maurya
,
Thomas
Bizien
,
Alice
Pincham
,
Andrew J.
Smith
,
Katsuaki
Inoue
,
Annela
Seddon
,
Massimo
Vassalli
,
Edward H.
Egelman
,
Dave J.
Adams
Diamond Proposal Number(s):
[37128, 37889]
Open Access
Abstract: Self-assembling peptides have great potential in nanotechnology. Here, we introduce the naphthalene-modified dipeptide isoleucine-phenylalanine (2NapIF) as a modular system for creating various nanostructures via self-assembly, including fibers, nanotubes, and bundles, resulting from the addition of salts. Mechanical stirring is crucial for developing certain supramolecular architectures. Using cryo-electron microscopy (cryo-EM), we found that the structural organization of these nanostructures is primarily driven by hydrophobic stacking of aromatic rings and hydrogen bonding among peptide atoms. The diversity in packing arises from the ability of 2NapIF to adopt multiple conformations, with our study revealing 18 distinct conformations within a KCl-induced nanotube. This results in a large asymmetric unit containing 18 molecules, with 18 conformations, that could never have been predicted with current tools. This modular system has potential applications in creating innovative materials, including robust, salt-responsive “noodles” that exceed a meter in length.
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Jul 2025
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[33006]
Open Access
Abstract: Understanding the assembly of small molecules in aqueous media is crucial for the development of adaptive biomaterials. The mechanical properties of supramolecular networks, including stiffness and stress relaxation, play a key role in cellular spreading and can be tuned via formulation strategies or monomer design. Here, we demonstrate the modulation of supramolecular polymerization and cellular response of ureidopyrimidinone (UPy) monomers in water by tailoring the length of the alkyl spacer within the monomer structure. A library of four UPy derivatives with varying hydrophilic–hydrophobic balances was synthesized by using an optimized synthetic approach. The assembly behavior and dynamics of the supramolecular polymers were investigated both in solution and gel states using a wide range of techniques. The results revealed that the alkyl spacer length significantly affects the supramolecular polymer dynamics, kinetics, and stability. Monomers with 6 and 8 methylene units formed dynamic elongated structures, while those with 10 and 12 units yielded robust and stable bundled fibers. In the gel state, a physical cross-linker was required for gel formation. The gels formed by the monomers featuring 8 and 10 methylene units exhibited optimal mechanical properties, promoting the spreading of human normal dermal fibroblasts in both 2D and 3D cultures. These findings highlight the impact of the monomer architecture on the properties of UPy supramolecular systems, paving the way for the rational design of biomaterials with tunable properties.
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Jun 2025
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[35286]
Open Access
Abstract: Benzophenone-based materials remain widely used as photoinitiators for ultraviolet light-induced free radical polymerizations. Traditionally, polymerization is spatially controlled using top-down techniques such as photomasks, which produce well-defined polymeric films. In contrast, we present an alternative method for controlling polymerization by employing supramolecular materials to localize the photoinitiator. This approach uses benzophenone-functionalized dipeptides that are specifically tuned to enable supramolecular gel noodle formation, which act as structural templates. We show that polymerization of acrylate monomers around the gel noodles can increase the Young’s modulus by up to 2 orders of magnitude and produce mechanically robust structures that can be handled. The self-assembly of the supramolecular photoinitiators is also explored using viscosity and SAXS measurements, providing an understanding of why only 4BPAcFF successfully forms gel noodles. Our method offers a simple yet effective technique for localizing polymerization, enabling fine-tuning of mechanical properties and the fabrication of intricate designs such as hollow-core structures.
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May 2025
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[21663]
Open Access
Abstract: Atmospheric aerosol hygroscopicity and reactivity play key roles in determining an aerosol's fate and are strongly affected by its composition and physical properties. Fatty acids are surfactants commonly found in organic aerosol emissions. They form a wide range of different nanostructures dependent on water content and mixture composition. In this study we follow nano-structural changes in mixtures frequently found in urban organic aerosol emissions, i.e. oleic acid, sodium oleate and fructose, during humidity change and exposure to the atmospheric oxidant ozone. Addition of fructose altered the nanostructure by inducing molecular arrangements with increased surfactant–water interface curvature. Small-angle X-ray scattering (SAXS) was employed for the first time to derive the hygroscopicity of each nanostructure, thus addressing a current gap in knowledge by measuring time- and humidity-resolved changes in nano-structural parameters. We found that hygroscopicity is directly linked to the specific nanostructure and is dependent on the nanostructure geometry. Reaction with ozone revealed a clear nanostructure–reactivity trend, with notable differences between the individual nanostructures investigated. Simultaneous Raman microscopy complementing the SAXS studies revealed the persistence of oleic acid even after extensive oxidation. Our findings demonstrate that self-assembly of fatty acid nanostructures can significantly impact two key atmospheric aerosol processes: water uptake and chemical reactivity, thus directly affecting the atmospheric lifetime of these materials. This could have significant impacts on both urban air quality (e.g. protecting harmful urban emissions from atmospheric degradation and therefore enabling their long-range transport) and climate (e.g. affecting cloud formation), with implications for human health and well-being.
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Dec 2024
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[32866]
Open Access
Abstract: Supramolecular systems are often designed such that a steady state exists. However, the ability to design systems with pre-determined changes in state can lead to highly dynamic materials, with evolving supramolecular structures and adaptable material properties. This approach is of great interest from the perspective of designing adaptive systems as well as from a broader systems chemistry perspective. Here, we report how a transient system can be altered to access different mechanical properties and transitions by varying the trigger and temperature. The aging of these systems is also explored, as the networks continually evolve long past the common cut-off point of analysis of one day. We therefore provide new insights into the control of transient gels, as well as an understanding as to the underpinning supramolecular structures and how they evolve with time.
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Nov 2024
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B21-High Throughput SAXS
I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[27906, 37100]
Open Access
Abstract: A long-standing challenge is how to formulate proteins and vaccines to retain function during storage and transport and to remove the burdens of cold-chain management. Any solution must be practical to use, with the protein being released or applied using clinically relevant triggers. Advanced biologic therapies are distributed cold, using substantial energy, limiting equitable distribution in low-resource countries and placing responsibility on the user for correct storage and handling. Cold-chain management is the best solution at present for protein transport but requires substantial infrastructure and energy. For example, in research laboratories, a single freezer at −80 °C consumes as much energy per day as a small household1. Of biological (protein or cell) therapies and all vaccines, 75% require cold-chain management; the cost of cold-chain management in clinical trials has increased by about 20% since 2015, reflecting this complexity. Bespoke formulations and excipients are now required, with trehalose2, sucrose or polymers3 widely used, which stabilize proteins by replacing surface water molecules and thereby make denaturation thermodynamically less likely; this has enabled both freeze-dried proteins and frozen proteins. For example, the human papilloma virus vaccine requires aluminium salt adjuvants to function, but these render it unstable against freeze–thaw4, leading to a very complex and expensive supply chain. Other ideas involve ensilication5 and chemical modification of proteins6. In short, protein stabilization is a challenge with no universal solution7,8. Here we designed a stiff hydrogel that stabilizes proteins against thermal denaturation even at 50 °C, and that can, unlike present technologies, deliver pure, excipient-free protein by mechanically releasing it from a syringe. Macromolecules can be loaded at up to 10 wt% without affecting the mechanism of release. This unique stabilization and excipient-free release synergy offers a practical, scalable and versatile solution to enable the low-cost, cold-chain-free and equitable delivery of therapies worldwide.
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Jul 2024
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I22-Small angle scattering & Diffraction
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Open Access
Abstract: Organic phosphates (OP) are important nutrient components for living cells in natural environments, where they readily interact with ubiquitous iron phases such as hydrous ferric oxide, ferrihydrite (FHY). FHY partakes in many key bio(geo)chemical reactions including iron-mediated carbon storage in soils, or iron-storage in living organisms. However, it is still unknown how OP affects the formation, structure and properties of FHY. Here, we document how β-glycerophosphate (GP), a model OP ligand, affects the structure and properties of GP–FHY nanoparticles synthesized by coprecipitation at variable nominal molar P/Fe ratios (0.01 to 0.5). All GP–FHY precipitates were characterized by a maximum solid P/Fe ratio of 0.22, irrespective of the nominal P/Fe ratio. With increasing nominal P/Fe ratio, the specific surface area of the GP–FHY precipitates decreased sharply from 290 to 3 m2 g−1, accompanied by the collapse of their pore structure. The Fe–P local bonding environment gradually transitioned from a bidentate binuclear geometry at low P/Fe ratios to monodentate mononuclear geometry at high P/Fe ratios. This transition was accompanied by a decrease in coordination number of edge-sharing Fe polyhedra, and the loss of the corner-sharing Fe polyhedra. We show that Fe(III) polymerization is impeded by GP, and that the GP–FHY structure is highly dependent on the P/Fe ratio. We discuss the role that natural OP-bearing Fe(III) nanophases have in biogeochemical reactions between Fe–P and C species in aquatic systems.
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Apr 2024
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[33006]
Open Access
Abstract: Light can be used to design stimuli-responsive systems. We induce transient changes in the assembly of a low molecular weight gelator solution using a merocyanine photoacid. Through our approach, reversible viscosity changes can be achieved via irradiation, delivering systems where flow can be controlled non-invasively on demand.
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Feb 2024
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