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At least 1,333 records · Page 74

Tubulin Double Helix: Lateral and Longitudinal Curvature Changes of Tubulin Protofilament

By virtue of their native structures, tubulin dimers are protein building blocks that are naturally pre-programmed to assemble into cytoskeletal polymers known as microtubules (MTs). Here we demonstrate polycation-directed (i.e. electrostatically tunable) assembly of tubulins through tubulin protofilament conformational changes in the longitudinal and lateral directions, creating novel tubulin double helices and various tubular architectures. Synchrotron small angle X-ray scattering and transmission electron microscopy reveal a remarkable range of nanoscale assembly structures: single- and double-layered double-helix tubulin tubules. The phase transitions from MTs into the new assemblies are dependent on the size and concentration of polycations. Two characteristic scales that determine the number of observed phases are the size of polycation compared to the size of tubulin (≈4 nm) and MT diameter (≈25 nm). This work suggests the feasibility of “programmable breakdown” of protein nanotubes, tearing MTs into double-stranded tubulins and building up previously undiscovered nanostructures, by using polycations with scissor- and glue-like properties. Importantly, we define a new role of tubulins as two-dimensionally shape-controllable building blocks for novel supramolecular architectures. Furthermore, these findings provide insight into the design of protein-based functional materials, for example, as metallization templates for nanoscale electronic devices, kinesin motor-driving molecular screws, and anticancer drug delivery vehicles.

2D shape‐control↗

Persistent Structure and Frustrated Magnetism in High Entropy Rare-Earth Zirconates

The configurational complexity and distinct local atomic environments of high entropy oxides remain largely unexplored, leaving structure-property relationships and the hypothesis that the family offers rich tunability for applications ambiguous. This work investigates the influence of cation size and materials synthesis in determining the resulting structure and magnetic properties of a family of high entropy rare-earth zirconates (HEREZs, nominal composition RE 2 Zr 2 O 7 with RE = rare-earth element combinations including Eu, Gd, Tb, Dy, Ho, La, or Sc). Here, the structural characterization of the series is examined through synchrotron X-ray diffraction and pair distribution function analysis, and electron microscopy, demonstrating average defect-fluorite structures with considerable local disorder, in all samples. The surface morphology and particle sizes are found to vary significantly with preparation method, with irregular micron-sized particles formed by high temperature sintering routes, spherical nanoparticles resulting from chemical co-precipitation methods, and porous nanoparticle agglomerates resulting from polymer steric entrapment synthesis. In agreement with the disordered cation distribution found across all samples, magnetic measurements indicate that all synthesized HEREZs show frustrated magnetic behavior, as seen in a number of single-component RE 2 Zr 2 O 7 pyrochlore oxides. These findings advance the understanding of the local structure of high entropy oxides and demonstrate strategies for designing nanostructured morphologies in the class.

36 MATERIALS SCIENCE↗

Electrochemistry of Thin Films with In Situ/Operando Grazing Incidence X-Ray Scattering: Bypassing Electrolyte Scattering for High Fidelity Time Resolved Studies

Electroactive polymer thin films undergo repeated reversible structural change during operation in electrochemical applications. While synchrotron X-ray scattering is powerful for the characterization of stand-alone and ex situ organic thin films, in situ/operando structural characterization has been underutilized-in large part due to complications arising from supporting electrolyte scattering. This has greatly hampered the development of application relevant structure property relationships. Therefore, a new methodology for in situ/operando X-ray characterization that separates the incident and scattered X-ray beam path from the electrolyte is developed. As a proof of concept, the operando structural characterization of weakly-scattering, organic mixed conducting thin films in an aqueous electrolyte environment is demonstrated, accessing previously unexplored changes in the $\pi-\pi$ peak and diffuse scatter, while capturing the solvent swollen thin film structure which is inaccessible in previous ex situ studies. These in situ/operando measurements improve the sensitivity to structural changes, capturing minute changes not possible ex situ, and have multimodal potential such as combined Raman measurements that also serve to validate the true in situ/operando conditions of the cell. Finally, new directions enabled by this in situ/operando cell design are examined and state of the art measurements are compared.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemically Dealloyed 3D Porous Copper Nanostructure as Anode Current Collector of Li-Metal Batteries

The commercialization of high-energy Li-metal batteries is impeded by Li dendrites formed during electrochemical cycling and the safety hazards it causes. Here, a novel porous copper current collector that can effectively mitigate the dendritic growth of Li is reported. This porous Cu foil is fabricated via a simple two-step electrochemical process, where Cu-Zn alloy is electrodeposited on commercial copper foil and then Zn is electrochemically dissolved to form a 3D porous structure of Cu. The 3D porous Cu layers on average have a thickness of ≈14 um and porosity of ≈72%. This current collector can effectively suppress Li dendrites in cells cycled with a high areal capacity of 10 mAh cm -2 and under a high current density of 10 mA cm -2 . This electrochemical fabrication method is facile and scalable for mass production. In conclusion, results of advanced in situ synchrotron X-ray diffraction reveal the phase evolution of the electrochemical deposition and dealloying processes.

36 MATERIALS SCIENCE↗

Amorphous K–Co–Mo–S x Chalcogel: A Synergy of Surface Sorption and Ion-Exchange

Chalcogel represents a unique class of meso- to macroporous nanomaterials that offer applications in energy and environmental pursuits. We report the synthesis of an ion-exchangeable amorphous chalcogel using a nominal composition of K 2 CoMo 2 S 10 (KCMS) at room temperature is reported. Synchrotron X-ray pair distribution function (PDF), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) reveal a plausible local structure of KCMS gel consisting of Mo 5+ 2 and Mo 4+ 3 clusters in the vicinity of di/polysulfides which are covalently linked by Co 2+ ions. The ionically bound K + ions remain in the percolating pores of the Co–Mo–S covalent network. XANES of Co K-edge shows multiple electronic transitions, including quadrupole (1s→3d), shakedown (1s→4p + MLCT), and dipole allowed 1s→4p transitions. Remarkably, despite a lack of regular channels as in some crystalline solids, the amorphous KCMS gel shows ion-exchange properties with UO 2 2+ ions. Additionally, it also presents surface sorption via [S∙∙∙∙UO 2 2+ ] covalent interactions. Overall, this study underscores the synthesis of quaternary chalcogels incorporating alkali metals and their potential to advance separation science for cations and oxo-cationic species by integrating a synergy of surface sorption and ion-exchange.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Monolayer TiS 2 Nanosheets on Au(111)–Structural Characterization and Effect of Edge Stability for Shape Control

Transition metal dichalcogenides are promising alternatives to noble metal catalysts, e.g., for (photo-)activation of greenhouse gases or hydrogenations. Herein, a direct synthetic route for 2D TiS 2 nanosheets on Au(111) by titanium deposition in the presence of a mild, organic, non-oxidizing sulfur source is presented. High-resolution scanning tunneling microscopy (STM) is used to gain atomic-level insights into the TiS 2 nanosheet morphology. In contrast to the literature, this protocol gains mostly hexagonal and truncated triangular nanosheets with an increased edge contrast in STM, analog to metallic edge states in MoS 2 . Synchrotron-based photoelectron spectroscopy allows insights into compositional details, specifically to distinguish different S sites on the TiS 2 sheets and other S species on the sample. Further, a minimum size is identified (9 S atoms side length), which underlines the importance of moiré reconstructions for stress relief. The TiS 2 sheets coexist with [Au]Ti 1 S 3 clusters, in which a single gold atom is alloyed into the surface and capped by three S atoms. Together with the finding of a critical sheet size, this points toward on-surface Ostwald ripening as a relevant process in the sheet formation. Ab-initio calculations (density functional theory) underscore that the chemical potential of S is an essential descriptor to maintain shape control.

2D nanomaterials↗

Interfacial and Kinetic Origins of Voltage Loss in Neutral Zinc‐Air Batteries

Rechargeable zinc-air batteries are promising candidates for grid-scale energy storage; however, their practical deployment is limited by oxygen electrocatalysis inefficiencies and interfacial instabilities, particularly outside conventional alkaline electrolytes. Here, in this work, zinc-air batteries operating under neutral electrolyte conditions using ZnCl 2 soaked KC-PAA-PAM gel polymer electrolytes and electrochemically synthesized Ni/Fe layered double hydroxide electrocatalysts is investigated. Ni/Fe-LDH is intentionally employed as an OER-biased benchmark catalyst to diagnose electrolyte and interface driven limitations rather than as a bifunctional ORR/OER solution. Full cells exhibit highly stable cycling over hundreds of hours, yet operate at substantially suppressed charge and discharge voltages relative to the thermodynamic value. Electrochemical impedance analysis shows that ohmic losses contribute only minimally to this voltage suppression. Post-mortem X-ray photoelectron spectroscopy reveals metallic zinc accumulation on the air cathode and chloride-containing species on the anode, indicating parasitic interfacial processes. Synchrotron-based soft X-ray absorption spectroscopy confirms stable Ni 2+ and Fe 3+ oxidation states during cycling, consistent with OER-biased catalytic behavior, while neutral-electrolyte oxygen evolution measurements demonstrate strong electrolyte-induced suppression of oxygen kinetics. Together, these results show that electrolyte chemistry and cathode-side parasitic processes, rather than catalyst identity alone, dominate voltage losses in neutral zinc-air batteries, providing mechanistic insight into the fundamental challenges associated with neutral electrolyte operation.

Long duration energy storage↗

Dynamic In‐Plane Heterogeneous and Inverted Response of Graphite to Fast Charging and Discharging Conditions in Lithium‐Ion Pouch Cells

Solutions for improving fast charging of lithium‐ion batteries have largely focused on alleviating through‐plane lithiation gradients while little is understood about in‐plane heterogeneities and how to resolve them. Herein, high‐speed synchrotron X‐ray diffraction (XRD) resolves graphite lithiation spatially and temporally during 6 C charging and 2 C discharging. At every point during operation, considerable differences in the state of lithiation across the pouch cell are present. Some regions are more responsive to operation than others, reaching full lithiation early during charge and full delithiation during discharge. Other regions within the cell never fully delithiate during discharge, despite a prolonged voltage hold at 2.8 V. Using time‐resolved XRD data, the calculated local current density (mA cm −2 ) at the graphite surface shows an unexpected occurrence of local inverted current densities where regions of graphite are observed to delithiate during charging and lithiate during discharging. A pseudo‐3D model is developed for the graphite electrode with spatially varying microstructural tortuosity to show how microstructural heterogeneity could influence spatial charge dynamics. The model could not predict the complex in‐plane charge behavior observed within the cell. Consequently physics‐based charging protocols based on homogeneous electrode assumptions may underestimate the local variations in charge dynamics and occurrence of lithium plating.

25 ENERGY STORAGE↗

Supercooling of Alaskan Beetle Larvae as a Winter Survival Strategy

Insects are able to survive subfreezing temperatures by either limiting ice crystal formation in their bodies or through freeze avoidance. Beetle larvae are able to avoid freezing in winter by dehydrating in the fall months and replacing their body water content with high concentrations of glycerol. This enables the body fluid of the insect to supercool, and even vitrify, recovering unharmed when the temperature warms in the spring. Using nondestructive, high‐energy X‐ray synchrotron diffraction experiments, direct insight into how cryopreservation occurs at the atomic level within the beetle larvae has been obtained. The results shed light on the molecular‐level interactions associated with the mechanism responsible for surviving freezing temperatures. The molecular models of severely dehydrated Alaskan beetle larvae, based on glycerol‐water mixtures, yield a total of 4.2 ± 1.2 intermolecular hydrogen bonds per glycerol molecule at 275 K, in good agreement with existing molecular dynamics simulations. Most importantly, they show that if just over half the body fluid content is water, the water clusters are too small to form ice crystals that cause cellular damage.

Benmore, Chris J. [X‐Ray Science Division Advanced↗

High‐Nickel Heterostructured Cathodes with Local Stoichiometry Control for High‐Voltage Operation

The growing demand for lithium‐ion batteries to power electric vehicles and other energy‐dense devices continues to fuel the need for cathodes of increasingly higher nickel in cathodes. The relentless pursuit of high Ni content, however, raises concerns on compromising cell lifetime and safety, especially under high‐voltage operation. Alternative to the traditional design of uniform or core–shell composition, we report a rational control of local stoichiometry in high‐Ni cathodes, enabling their high thermal and cycling stabilities—up to 258 °C at the fully charged state and 91.4% capacity retention for 100 cycles between 2.7 and 4.4 V. Multimodal synchrotron X‐ray characterization unveils the heterostructure of secondary particles, featuring a high‐Ni core (LiNi 0.90 Mn 0.05 Co 0.05 O 2 ) covered by a thin Ni‐gradient layer that remains stable over prolonged cycling due to suppressed oxygen release and structural deterioration. This work underlines, the intricate interplay between local stoichiometry and redox reactions in stabilizing high‐Ni cathodes for high‐voltage operation while ensuring safety.

36 MATERIALS SCIENCE↗

Soft X‐Ray Absorption Spectroscopy With a Flat Liquid Jet in Vacuum Using a Table‐Top Laser‐Induced Plasma Source

ABSTRACT In this work, we demonstrate the integration of a flat liquid jet sample delivery system into a compact soft x‐ray absorption spectrometer using a table‐top laser‐induced plasma source. A high‐speed flat liquid sheet is formed by the collision of two cylindrical jets. This micrometer‐thin lamella can ideally be utilized for transmission‐mode soft x‐ray absorption spectroscopy using krypton plasma emission. Detailed analysis of the jet's thickness profile is achieved applying Lambert–Beer's law. Measurements on water, focusing on the oxygen K‐edge, reveal a lamella thickness profile ranging from 500 nm to 1 μm over a length of 3.8 mm. Additionally, we have investigated aqueous solutions of iron salts, capturing near edge x‐ray absorption fine structure spectra over a broad spectral range from the nitrogen K‐edge to the iron L‐edge. Focused analysis on iron species in aqueous solutions enabled us to distinguish quantitatively between the oxidation states of Fe 2+ and Fe 3+ at the iron L‐edge. Our results are compared with measurements obtained under similar conditions at a synchrotron.

Holburg, Jonathan [Department Optics/Short Wavelen↗

Universally Accessible Structural Data on Macromolecular Conformation, Assembly, and Dynamics by Small Angle X-Ray Scattering for DNA Repair Insights.

Structures provide a critical breakthrough step for biological analyses, and small angle X-ray scattering (SAXS) is a powerful structural technique to study dynamic DNA repair proteins. As toxic and mutagenic repair intermediates need to be prevented from inadvertently harming the cell, DNA repair proteins often chaperone these intermediates through dynamic conformations, coordinated assemblies, and allosteric regulation. By measuring structural conformations in solution for both proteins, DNA, RNA, and their complexes, SAXS provides insight into initial DNA damage recognition, mechanisms for validation of their substrate, and pathway regulation. Here, we describe exemplary SAXS analyses of a DNA damage response protein spanning from what can be derived directly from the data to obtaining super resolution through the use of SAXS selection of atomic models. We outline strategies and tactics for practical SAXS data collection and analysis. Making these structural experiments in reach of any basic and clinical researchers who have protein, SAXS data can readily be collected at government-funded synchrotrons, typically at no cost for academic researchers. In addition to discussing how SAXS complements and enhances cryo-electron microscopy, X-ray crystallography, NMR, and computational modeling, we furthermore discuss taking advantage of recent advances in protein structure prediction in combination with SAXS analysis.

Chinnam, Naga Babu↗

Limits on dark matter annihilation from the shape of radio emission in M31

Well-motivated models of dark matter often result in a population of electrons and positrons within galaxies produced through dark matter annihilation — usually in association with gamma rays. As they diffuse through galactic magnetic fields, these e ± produce synchrotron radio emission. The intensity and morphology of this signal depends on the properties of the interstellar medium through which the e ± propagate. Using observations of the Andromeda Galaxy (M31) to construct a model of the gas, magnetic fields, and starlight, we set constraints on dark matter annihilation to b$\overline{b}$ using the morphology of 3.6 cm radio emission. As the emission signal at the center of M31 is very sensitive to the diffusion coefficient and dark matter profile, we base our limits on the differential flux in the region between 0.9 – 6.9 kpc from the center. We exclude annihilation cross sections ≳ 3 × 10 −25 cm 3 /s in the mass range 10 – 500 GeV, with a maximum sensitivity of 7 × 10 −26 cm 3 /s at 20 – 40 GeV. Though these limits are weaker than those found in previous studies of M31, they are robust to variations of the diffusion coefficient.

79 ASTRONOMY AND ASTROPHYSICS↗

Archeological wood conservation with selected organosilicon compounds studied by XFM and nanoindentation

Waterlogged wood conservation is a complex and challenging task. Detailed knowledge about the interactions between the applied chemicals and wood is necessary to ensure the effective and safe conservation of wooden artifacts. The present research aims to determine the mechanism of dimensional stabilization of archeological wood by organosilicon compounds using the combination of synchrotron-based X-ray fluorescence microscopy (XFM) and nanoindentation. Archeological oak wood was treated with methyltrimethoxysilane, (3-mercaptopropyl)trimethoxysilane, or 1,3-bis-[(diethylamino)-3-(propoxy)propan-2-ol]-1,1,3,3-tetramethyldisiloxane, which in previous studies were found to be more effective than other organosilicons in stabilizing wood dimensions. The XFM and nanoindentation results showed that all three organosilicons infiltrated wood cell walls and enhanced their mechanical properties. The XFM also showed that part of the chemicals filled some void spaces like cell lumina. Based on the results obtained here and in our previous research, it is determined that the mechanism of archeological wood dimensional stabilization by organosilicon treatment is complex and likely involves both filling cell lumina and infiltration into cell walls where organosilicons interact with wood polymers.

59 BASIC BIOLOGICAL SCIENCES↗

Conservation of model degraded pine wood with selected organosilicons studied by XFM and nanoindentation

Previous research found that some organosilicon treatments proved effective in stabilizing waterlogged wood dimensions during drying. The present research aimed to determine the mechanism of wood stabilization by these chemicals to understand their mode of action. Here, the study used chemically (ChP) and biologically degraded (BP) model Scots pine wood treated with Methyltrimethoxysilane (MTMS), (3-Mercaptopropyl) trimethoxysilane (MPTMS), or 1,3-Bis(diethylamino)-3-propoxypropanol)-1,1,3,3-tetramethyldisiloxane (DEAPTMDS). Synchrotron-based X-ray fluorescence microscopy (XFM) was used to investigate the penetration of organosilicons into the wood cellular structure and cell walls, and nanoindentation was used to study the mechanical properties of the treated wood cell walls. All treatments resulted in high volumetric anti-shrink efficiency (ASE V ) values of 74-82%, except for MTMS-treated ChP with an ASE V of 52%. The multiscale XFM results revealed that all applied organosilicons penetrated throughout the whole wooden blocks and deposited in both cell lumina and cell walls. The retention of all applied organosilicons was highest in BP wood, and so was the dimensional stabilization effect. MTMS-treated ChP had the lowest measured cell wall infiltration, which likely contributed to its lower ASE v . DEAPTMDS treatments plasticized the cell walls and resulted in lowered nanoindentation elastic modulus (E s NI ) and hardness (H) for all types of wood. MTMS and MPTMS had modest effects on cell wall mechanical properties, and the effect depended on the type of wood. The final effect of organosilicon treatment on the dimensional wood stabilization and mechanical properties of wood cell walls depended not only on the type of the applied organosilicon but also the type of wood degradation. This means that the treatment cannot be considered universal, and specific approaches are needed for the conservation of individual wooden objects. Although some mechanisms are now better understood, such as the need for organosilicons to infiltrate the cell walls and the plasticizing effect of DEAPTMDS, other aspects will benefit from a more detailed analysis of the molecular interactions between organosilicons and wood polymers.

59 BASIC BIOLOGICAL SCIENCES↗

Structure and thermodynamics of calcium rare earth silicate oxyapatites, Ca 2 RE 8 (SiO 4 ) 6 O 2 (RE = Pr, Tb, Ho, Tm)

Calcium rare earth silicate oxyapatites, (Ca 2 RE 8 (SiO 4 ) 6 O 2 ), are of interest as components of glass-ceramic nuclear waste forms. To assess their long-term behavior in a geologic repository, it is essential to determine their structure and thermodynamic stability at relevant conditions. Here, in this work, we performed detailed structural and thermodynamic investigations on Ca 2 Pr 8 (SiO 4 ) 6 O 2 , Ca 2 Tb 8 (SiO 4 ) 6 O 2 , Ca 2 Ho 8 (SiO 4 ) 6 O 2 , and Ca 2 Tm 8 (SiO 4 ) 6 O 2 by high energy synchrotron powder X-ray diffraction combined with Rietveld analysis and high temperature oxide melt drop solution calorimetry. Enthalpies of formation from constituent oxides (ΔH f,ox ) were determined to be -765.1 ± 22.8 kJ/mol for Ca 2 Pr 8 (SiO 4 ) 6 O 2 ; -638.9 ± 20.5 kJ/mol for Ca 2 Tb 8 (SiO 4 ) 6 O 2 ; -643.3 ± 10.3 kJ/mol for Ca 2 Ho 8 (SiO 4 ) 6 O 2 ; and -403.2 ± 5.1 kJ/mol for Ca 2 Tm 8 (SiO 4 ) 6 O 2 . These thermodynamic parameters were used in assessing the thermochemical stability of these phases in the presence of water vapor from room temperature to 600 K, as encountered in the subsurface environments of a geological repository.

36 MATERIALS SCIENCE↗

Control of deviatoric stress in the diamond anvil cell through thermal expansion mismatch stress in thin films

Elastic and plastic properties of materials and phase transitions at extreme conditions vary with both hydrostatic pressure and deviatoric stress. To generate and measure controlled deviatoric stress at pressures beyond those accessible with large volume differential and rotational presses and optical access for spectroscopy, experiments tested the combination of diamond anvil cell and thin film technology. Thin films of polycrystalline Cr-doped Al 2 O 3 ruby were prepared using pulsed laser deposition on single-crystal substrates of either Al 2 O 3 sapphire or yttria-stabilized cubic zirconia for contrasting initial film stress, and loaded in diamond anvil cells for confining stress. The piezospectroscopic response of the ruby films demonstrates consistently higher deviatoric stress in the film on zirconia relative to the film on the control sapphire, and an increase in deviatoric stress with applied load. Complementary synchrotron X-ray diffraction of the zirconia substrate confirmed that no pressure-induced phase transitions impacted the stress state of the ruby film, but differences in compressibility of film and substrate result in changes in film stress analogous to thermal expansion mismatch. Furthermore, this technique may be applied to evaluate elastic and plastic response of thin films of a variety of materials under extreme stress.

36 MATERIALS SCIENCE↗

Lattice dynamics, sound velocities, and atomic environments of szomolnokite at high pressure

Complex mixtures of sulfates, silicates, and ice have been observed in a variety of planetary environments on Earth, Mars and the icy satellites of the solar system. Characterizing the properties of the corresponding compositional endmembers is important for understanding the interiors of a range of planetary bodies in which these phases are observed. To measure the electronic and vibrational properties of the pure ferrous iron endmember of the kieserite group, szomolnokite, (FeSO 4 ∙H 2 O), we have performed synchrotron 57 Fe nuclear resonant inelastic and forward scattering experiments in the diamond-anvil cell up to 14.5 GPa. This pressure range covers depths within Earth’s interior relevant to sulfur cycling in subduction zones and the range of pressures expected within icy satellite interiors. We find evidence of crystal lattice softening, changes in elastic properties, and changes in the electric field gradients of iron atoms associated with two structural transitions occurring within the experimental pressure range. Here we apply these findings to icy satellite interiors, including discussion of elastic properties, modeling of ice-sulfate aggregates, and implications for tidal observations.

58 GEOSCIENCES↗