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At least 73 records · Page 4

Structure and Sulfur: Tuning the Viscoelastic and Surface Properties of Natural Keratin Fibers

Natural keratin fibers, such as wool, possess a complex hierarchical structure that governs their mechanical properties and surface energy. However, the extent to which these characteristics are influenced by combined contributions of structural variations (e.g., fiber diameter, intermediate filament (IF) packing) and chemical composition (e.g., disulfide bond density) remains poorly understood. In this study, we investigate wool fibers from five sheep breeds (Merino, Polwarth, Cheviot, Eider, and Devon) to elucidate how these factors influence viscoelasticity and surface interactions. Using a multimodal approach integrating interfacial and bulk characterization methods, including inverse gas chromatography (IGC), atomic force microscopy-infrared spectroscopy (AFM-IR), X-ray photoelectron spectroscopy (XPS), uniaxial tensile testing, and synchrotron small-angle X-ray scattering (SAXS), we show that the nanometer-thick 18-methyleicosanoic acid (18-MEA) layer is consistently present across all wool types and plays a key role in governing hydrophobicity and surface heterogeneity. A controlled isothermal treatment at 200 °C, designed to cleave disulfide bonds, results in a nearly 40% reduction in specific surface area across all fiber types, accompanied by a significant decrease in tensile strength and 80% reduction in elongation at break for Merino and Devon wool, but limited influence on the mechanical properties of Eider fibers. Furthermore, rate-dependent tensile testing within the elastic regime reveals distinct viscoelastic responses among the fiber types, suggesting that the sulfur-rich protein matrix surrounding IFs and its structure contribute actively to stress partitioning. Altogether, when combined with conclusions from SAXS measurements of IF spacing, our work offers compelling insights into the role of the keratin-associated protein (KAP) matrix in shaping wool fiber mechanics. Differences in mechanical behavior among wool types, despite similar IF spacing or sulfur content, highlight the importance of matrix composition and cross-linking density, suggesting that the molecular architecture of the KAP network may be a dominant factor in determining fiber performance.

X-ray scattering

Structural Transformation and Degradation of Cu Oxide Nanocatalysts during Electrochemical CO 2 Reduction

The electrochemical CO 2 reduction reaction (CO 2 RR) holds enormous potential as a carbon-neutral route to the sustainable production of fuels and platform chemicals. The durability for long-term operation is currently inadequate for commercialization, however, and the underlying deactivation process remains elusive. A fundamental understanding of the degradation mechanism of electrocatalysts, which can dictate the overall device performance, is needed. In this work, we report the structural dynamics and degradation pathway of Cu oxide nanoparticles (CuO x NPs) during the CO 2 RR by using in situ small-angle X-ray scattering (SAXS) and X-ray absorption spectroscopy (XAS). The in situ SAXS reveals a reduction in the size of NPs when subjected to a potential at which no reaction products are detected. At potentials where the CO 2 RR starts to occur, CuO x NPs are agglomerated through a particle migration and coalescence process in the early stage of the reaction, followed by Ostwald ripening (OR) as the dominant degradation mechanism for the remainder of the reaction. As the applied potential becomes more negative, the OR process becomes more dominant, and for the most negative applied potential, OR dominates for the entire reaction time. The morphological changes are linked to a gradual decrease in the formation rate for multicarbon products (C 2 H 4 and ethanol). Other reaction parameters, including reaction intermediates and local high pH, induce changes in the agglomeration process and final morphology of the CuO x NPs electrode, supported by post-mortem ex situ microscopic analysis. The in situ XAS analysis suggests that the CuO x NPs reduced into the metallic state before the structural transformation was observed. The introduction of high surface area carbon supports with ionomer coating mitigates the degree of structural transformation and detachment of the CuO x NPs electrode. These findings show the dynamic nature of Cu nanocatalysts during the CO 2 RR and can serve as a rational guideline toward a stable catalyst system under electrochemical conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Deciphering supramolecular and polymer-like behavior in metallogels: real-time insights into temperature-modulated gelation and rapid self-assembly dynamics

Bis(pyridyl) urea-based gelators, namely L2 and its isomeric mixture ( L1 + L2 ), are known to self-assemble into 1D architectures capable of inducing supramolecular gelation. Coordination with metal ions such as Ag( I ), Cu( II ), and Fe( III ) introduces structural reinforcement, enabling the formation of distinct 3D networks governed by metal-specific coordination geometries. Here, we present a comprehensive investigation into the temperature-responsive behavior (20–60 °C) of L2 and L1 + L2 , both in the absence and presence of Ag( I ), Dy( III ), Fe( III ), Cu( II ), and Ho( III ), using real-time small-angle neutron scattering (SANS). To probe long-term structural evolution/kinetics of self-assembly, real-time small-angle X-ray scattering (SAXS) was employed on L2 + Ag gels, complemented by differential scanning calorimetry (DSC) to evaluate thermal transitions. Our results reveal strikingly divergent gelation behaviors: L2 forms a highly rigid, covalent polymer-like network, while L1 + L2 exhibits remarkable thermal adaptability. Upon metal coordination, the assemblies exhibit pronounced crystallinity and exceptional thermal stability, as evidenced by persistent Bragg reflections and invariant d-spacings. Intriguingly, L2 : Fe (2 : 1) and L1 : L2 : Fe (0.5 : 0.5 : 1) in acetonitrile-d 3 (ACN-d 3 ) deviate from this trend, forming thermally labile amorphous gels. These systems show a complete loss of crystalline order, reduced Porod exponents—indicative of collapsed or branched fiber morphologies—and prominent melting and glass transition events in DSC. Fitting SANS and SAXS data to the correlation length model unveiled insightful nanostructural features. While most systems displayed minimal temperature-induced variation in mesh size or surface morphology, L2 : Ag in dimethyl sulfoxide-d 6 (DMSO-d 6 )/D 2 O and L2 : Fe (1 : 1) in ACN-d 3 exhibited a rare combination of thermally stable correlation lengths and increasing high- q exponents—strongly suggesting progressive fiber densification or surface smoothing within a robust gel framework. These findings highlight the tunability and structural resilience of supramolecular gels through precise control of ligand architecture, metal coordination, and temperature, offering valuable design principles for functional soft materials.

Pajoubpong, Jinnipha [Univ. of Cincinnati, OH (Uni

Early events in G-quadruplex folding captured by time-resolved small-angle X-ray scattering

Abstract Time-resolved small-angle X-ray experiments are reported here that capture and quantify a previously unknown rapid collapse of the unfolded oligonucleotide as an early step in the folding of hybrid 1 and hybrid 2 telomeric G-quadruplex structures. The rapid collapse, initiated by a pH jump, is characterized by an exponential decrease in the radius of gyration from 24.3 to 12.6 Å. The collapse is monophasic and is complete in <600 ms. Additional hand-mixing pH-jump kinetic studies show that slower kinetic steps follow the collapse. The folded and unfolded states at equilibrium were further characterized by SAXS studies and other biophysical tools, showing that G4 unfolding was complete at alkaline pH, but not in LiCl solution as is often claimed. The SAXS Ensemble Optimization Method analysis reveals models of the unfolded state as a dynamic ensemble of flexible oligonucleotide chains with a variety of transient hairpin structures. These results suggest a G4 folding pathway in which a rapid collapse, analogous to molten globule formation seen in proteins, is followed by a confined conformational search within the collapsed particle to form the native contacts ultimately found in the stable folded form.

Biochemistry & Molecular Biology

Insights on carbon dioxide adsorption in a flexible 1-D coordination polymer from in situ X-ray scattering and density functional theory

A combination of in situ small-angle X-ray scattering (SAXS) microstructure characterization over scales ranging from 1 nm to 10 µm and powder X-ray diffraction (XRD) structure characterization under various gas/pressure/temperature conditions with density functional theory (DFT) calculations provides new insights for the CO2 sorption behavior of a one-dimensional porous coordination polymer: catena-bis­(di­benzoyl­methanato)(4,4′-bi­pyridyl)­nickel(II), denoted NiDBM-Bpy. The NiDBM-Bpy chains are held together by van der Waals forces, but the structure of guest-free NiDBM-Bpy is unsolved due to a lack of suitable crystals and high-quality powder XRD patterns. Nevertheless, SAXS and powder XRD can follow microstructural and structural changes as a function of gas pressure, composition and temperature. Both mixed-gas flow and static supercritical CO2 regimes are explored experimentally. DFT calculations are used to model the structural variation associated with XRD changes and hysteresis in the sorption isotherms. XRD and DFT calculations suggest that an orthorhombic Fddd structure with two CO2 per Ni emerges following a transition from the structure with lower molar volume and symmetry that exists without CO2 present.

Allen, Andrew J.

Autonomous Infrared and Small (Wide) Angle X-Ray Scattering (IR-S(W)AXS) Capability

Thin water films are 2-D, nanoconfined layers that form on solid surfaces exposed to humid atmospheres—environments ubiquitous across catalysis, corrosion science, soil science, and subsurface geochemistry. At relative humidity (RH) values below saturation, these films are Å–nm thick and exhibit properties that differ sharply from bulk water, including disrupted H-bonding and impeded mass transport. Owing to their high surface-to-volume ratio, dissolution of the solid can rapidly drive strong supersaturation with respect to secondary phases. Reactivity in thin water films is highly sensitive to film thickness, and critically, thickness evolves during reaction because the hygroscopicity of the interfacial system changes as ions accumulate or diminish in the film and as reaction products transform. To accurately probe and control these dynamics, a capability is needed that can measure and automatically maintain a constant water-film thickness while simultaneously monitoring solid dissolution, nucleation, and growth. This project developed an autonomous Infrared/Small Angle X-ray Scattering-Wide Angle X-ray Scattering (IR/(W)SAXS) for investigating reactivity in thin water films on solid surfaces exposed to humidified gases. The capability consists of an IR spectrometer, a (W)SAXS instrument, and a mass flow controller system for generating variably humidified gas flows to a custom reaction cell. Progress on each of the major components of the capability are detailed below.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND

Homogeneous versus heterogeneous crystal nucleation in Li2O-2SiO2 glass

When analyzing crystal nucleation in glasses, it is difficult to distinguish between homogeneous and heterogeneous nucleation. A method is proposed to investigate the nature of crystal nucleation in Li2O-2SiO2, and calculations are performed to determine under which conditions saturation effects help ascertain the nature of the nucleation. The capability of detecting impurity particles in unheated glass via standard micrographic techniques (SEM or REM) and small angle X-ray scattering (SAXS) is explored. Results indicate that if the maximum impurity particle densities do not exceed 2 x 10 to the 7th per cu cm then heterogeneous nucleation may be excluded and most impurity particles with densities in excess of 10 to the 10th per cu cm are detectable by SAXS. It is concluded that crystal nucleation in this system most probably occurs homogeneously.

Weinberg, M. C.

The New BeppoSAX Observation of the Brightest X-Ray Quasar at Redshift

This grant was to support the reduction and analysis of our approved SAX observation of the high redshift (z=3.2) blazar PKS 2126-158. This is the brightest quasar at z greater than 3 and has been intensively studied in X-ray, since the first Einstein detection. In 1994 Elvis et al., discovered a strong low energy cutoff in this object, which could imply either quasar frame photoelectric absorption by a column of 0.8-2.7 x 1e22 cm-2 cold gas, or a lower column of cold gas at z=0. Subsequent ASCA observations of this object, could not definitely address this issue, nor could establish whether the curvature of the low energy portion of the spectrum was due to pure photoelectric absorption (considerably exceeding the Galactic value along the line of sight) or to an intrinsic continuum curvature. We proposed to observe PKS 2126-158 with BeppoSAX, to try to solve this puzzle (thanks to the broadband of BeppoSAX: 0.1-250 keV). PKS 2126 was observed by BeppoSAX on May 1999, with a MECS exposure of 100 ks. We have reduced and analyzed the BeppoSAX data, and compared them with a Chandra ACIS observation of the same object, taken only 6 months apart (Nov. 1999). We have recently finished to write a paper on the BeppoSAX data only, that concentrate on the properties of the X-ray absorber, which is highly requested by our SAX data, independently on the continuum model adopted. The paper (P.I.F. Fiore) will be submitted to APJ in the next few days. A second paper on the combined BeppoSAX and Chandra data, and based on the broad band spectral energy distribution of this quasar, is currently in preparation. Our main results, on the X-ray absorber, are: (a) the presence of an X-ray absorber is confirmed, indipendently on the continuum adopted (simple power law, or curved continuum); (b) if the absorber is not significantly ionized, then the BeppoSAX data do prefer a low redshift absorber; (c) if the gas is ionized, then it can be located in the quasar environment, but its metal abundances must be lower than 0.2 times solar (because of the absence of a strong FeK absorption edges that would follow at approx. 2 keV, where the MECS response is the highest).

Nicastro, Fabrizio

A Spectral Study of a New Class of Radio Quasars

This document serves as a final technical report for NASA grants NAG5-9995 and NAG5-9533, entitled 'A Spectral Study of a New Class of Radio Quasars.' The purpose of these grants were to support observations made using the BeppoSAX satellite. The observations took place over two years and covered two SAX observing cycles, respectively AO-3 and AO-4. During this time, I was employed both at Johns Hopkins University (NAG5-9995) and the University of Maryland, Baltimore County (NAG5-9533). As the research on these grants was on the same subject and my employment at JHU and UMBC has been consecutive, this document therefore covers both grants. The targets for these observations were four radio-loud quasars chosen from the first two X-ray selected samples of such objects. These were the brightest examples of the newly found class of X-ray loud flat-spectrum radio quasars, which prior to 1997, had never been seen before. However, my previous work with collaborators Paolo Padovani and Paolo Giommi on the DXRBS survey showed that they make up about 25% of the population of flat-spectrum radio quasars, but had not been seen before because of selection biases (all previous samples of these objects had been compiled in the radio). The purpose of the SAX observations was to investigate the shape of their X-ray spectrum, which would tell us where the peak of their synchrotron emission was located.

Perlman, Eric S.

New digital measurement methods for left ventricular volume using real-time three-dimensional echocardiography: comparison with electromagnetic flow method and magnetic resonance imaging

AIM: The aim of this study was to investigate the feasibility and accuracy of using symmetrically rotated apical long axis planes for the determination of left ventricular (LV) volumes with real-time three-dimensional echocardiography (3DE). METHODS AND RESULTS: Real-time 3DE was performed in six sheep during 24 haemodynamic conditions with electromagnetic flow measurements (EM), and in 29 patients with magnetic resonance imaging measurements (MRI). LV volumes were calculated by Simpson's rule with five 3DE methods (i.e. apical biplane, four-plane, six-plane, nine-plane (in which the angle between each long axis plane was 90 degrees, 45 degrees, 30 degrees or 20 degrees, respectively) and standard short axis views (SAX)). Real-time 3DE correlated well with EM for LV stroke volumes in animals (r=0.68-0.95) and with MRI for absolute volumes in patients (r-values=0.93-0.98). However, agreement between MRI and apical nine-plane, six-plane, and SAX methods in patients was better than those with apical four-plane and bi-plane methods (mean difference = -15, -18, -13, vs. -31 and -48 ml for end-diastolic volume, respectively, P<0.05). CONCLUSION: Apically rotated measurement methods of real-time 3DE correlated well with reference standards for calculating LV volumes. Balancing accuracy and required time for these LV volume measurements, the apical six-plane method is recommended for clinical use.

Evaluation Studies

On the 2018 Outburst of the Accreting Millisecond X-Ray Pulsar Swift J1756.9-2508 As Seen with NICER

We report on the coherent timing analysis of the 182 Hz accreting millisecond X-ray pulsar SwiftJ1756.92508during its 2018 outburst as observed with the Neutron Star Interior Composition Explorer (NICER). Combiningour NICER observations with Rossi X-ray Timing Explorer observations of the 2007 and 2009 outbursts, we alsostudied the long-term spin and orbital evolution of this source. We find that the binary system is well describedby a constant orbital period model, with an upper limit on the orbital period derivative of Pb < 7.4 ´ 10-13 ss1.Additionally, we improve upon the source coordinates through astrometric analysis of the pulse arrival times,finding R.A.=17h56m57 18±0 08 and decl.=25°0627 8±3 5, while simultaneously measuring thelong-term spin frequency derivative as n = -7.3 ´ 10-16 Hzs1. We briefly discuss the implications of thesemeasurements in the context of the wider population of accreting millisecond pulsars. We reported on the coherent timing analysis of the 2018 outburst of Swift J1756 as observed with NICER. Consistent with analyses of the previous outbursts (Krimm et al. 2007b; Patruno et al. 2010), we find that the X-ray pulsations have energy dependent amplitudes; the fractional amplitude of the fundamental increases with energy, whereas the fractional amplitude of the harmonic shows a slight decline with energy. This energy dependent behavior is not unusual in AMXPs (Patruno & Watts 2012) and can be interpreted in terms of the thermal emission from the stellar hotspot and reprocessing in the accretion column (e.g., Gierliński et al. 2002; Ibragimov & Poutanen 2009). The pulse arrival times of the 2018 outburst are well described by a timing model consisting of a circular orbit with a constant spin frequency. The pulse phases with respect to this model do not show spurious residuals with time or orbital phase, and no evidence is found that the pulse arrival times exhibit an additional delay associated with passing through the gravitational well of the companion star (Shapiro delay). We note, however, that the expected Shapiro delay is given as (Shapiro et al. 1971) Equation (5) where Φ is the orbital phase, G is the gravitational constant, c is the speed of light, and i is the inclination. Even for the maximum allowed companion mass, ${M}_{C}=0.030\,{M}_{\odot }$ (Krimm et al. 2007b, but see Section 4.2 for more details) and an inclination of 90°, the largest delay we can expect is only 4 μs. As this time-delay is smaller than the uncertainty on our phase residuals by nearly two orders of magnitude (see Figure 1), we are not sensitive to Shapiro delays in Swift J1756. Comparing our measurements for the 2018 outburst with those of the 2007 and 2009 outbursts as observed with RXTE, we analyzed the long-term evolution of this source. We found that the binary system is consistent with having a constant orbital period and that the pulsar shows a spin frequency derivative of $\dot{\nu }=-7.3\times {10}^{-16}\,\mathrm{Hz}\,{{\rm{s}}}^{-1}$. 4.1. Spin-down Evolution The long-term spin frequency derivative measured in Swift J1756 is of the same order as the spin frequency derivatives measured in other AMXPs (Hartman et al. 2008; Patruno 2010; Riggio et al. 2011). This frequency change is most likely driven by the neutron star's loss of rotational energy. If so, then the spin-down luminosity is given as Equation (6) where I represents the neutron star moment of inertia. The long-term spin-down of a neutron star is usually assumed to be dominated by the braking torque associated with a spinning magnetic field. Assuming this mechanism is responsible for the observed spin-down in Swift J1756, we can compute the magnetic dipole moment as (Spitkovsky 2006) Equation (7) where α is the misalignment angle between the rotational and magnetic poles. Considering α = 0°–90°, we then find a magnetic field strength of $B\simeq (4\mbox{--}6)\times {10}^{8}$ G at the stellar magnetic poles. This magnetic field strength estimate is in line with those obtained for other accreting millisecond pulsars (see Mukherjee et al. 2015 and references therein). 4.2. Orbit Evolution The observed long-term binary evolution of Swift J1756 is consistent with this source having a constant orbital period and a lower limit on the evolutionary timescale of Equation (8) Binary evolution theory predicts that systems of this type evolve due to angular momentum loss through gravitational radiation (Kraft et al. 1962; Rappaport et al. 1982; Verbunt 1993). For conservative mass transfer, the binary period derivative is given by di Salvo et al. (2008), Equation (9) where MNS is the neutron star mass, $q={M}_{C}/{M}_{\mathrm{NS}}$ is the binary mass ratio, and −1/3 < n < 1 is the mass–radius index of the companion star. Depending on the source inclination, Krimm et al. (2007b) derived a companion mass of ${M}_{C}\,=0.007\mbox{--}0.022\,{M}_{\odot }$ for a neutron star mass of 1.4 ${M}_{\odot }$. For a neutron star mass of 2.2 ${M}_{\odot }$, the allowed range increased to ${M}_{C}=0.009\mbox{--}0.030\,{M}_{\odot }$. In both cases, they assumed an upper limit on the inclination of i < 85°, motivated by the fact that Swift J1756 does not show eclipses in its light curve. Accounting for the extreme cases of stellar masses and n, the binary may either be contracting or expanding. In either case, however, the rate of change is limited to $| {\dot{P}}_{b}| \lesssim 7\times {10}^{-14}$ s s−1, which is well below the upper limit obtained in this work. Although the binary evolution timescale we obtain for Swift J1756 is consistent with theory, it is worth noting that this is not generally true for low-mass X-ray binaries (see Patruno et al. 2017, for a comprehensive discussion). The AMXP SAX J1808.4–3658, in particular, has been found to evolve on a much shorter timescale, with a first derivative on the orbital period of $3.5\times {10}^{-12}$ s s−1 (Hartman et al. 2008; Patruno et al. 2012; Sanna et al. 2017a). Two models have been proposed to explain this discrepancy: highly nonconservative mass transfer due to irradiation of the companion star by the pulsar (di Salvo et al. 2008; Burderi et al. 2009), and spin–orbit coupling in the companion star (Hartman et al. 2008, 2009). While the latter depends on the companion star, and may vary from source to source, the former should operate in all AMXPs (see also Patruno 2017; Sanna et al. 2017c), including Swift J1756. The spin-down luminosity impinging on the companion star can be estimated as Equation (10) where ${\dot{E}}_{\mathrm{abl}}$ is the ablation luminosity, RL2 is the Roche lobe radius of the companion (Eggleton 1983), and a the binary separation. The irradiation fraction is $f={\dot{E}}_{\mathrm{abl}}/{\dot{E}}_{\mathrm{sd}}$, which, accounting for the range of allowed neutron star and companion masses, evaluates to f = 0.15%–0.35%. The associated mass loss for the companion is given by Equation (11) such that, assuming an efficiency of η = 100%, ${\dot{M}}_{C}\,\sim -3\times {10}^{-10}\,{M}_{\odot }$ yr−1. The effect of this mass loss on the orbital period follows through the relation (Frank et al. 2002) Equation (12) giving a period derivative due to mass loss of ${\dot{P}}_{b,\mathrm{ML}}\,=5\times {10}^{-12}$ s s−1. This value is well above our limit on the period derivative. Hence, in order for this mechanism to be consistent with our observations of Swift J1756, the efficiency at which the companion star converts the incident luminosity into mass loss must be η < 15%. This value is very different from the 40% required in SAX J1808.4–3658 (Patruno et al. 2016) and is instead in line with the <5% efficiency determined for IGR J00291+5934 (Patruno 2017). This work was supported by NASA through the NICER mission and the Astrophysics Explorers Program, and made use of data and software provided by the High Energy Astrophysics Science Archive Research Center (HEASARC). P.B. was supported by an NPP fellowship at NASA Goddard Space Flight Center. D.A. acknowledges support from the Royal Society.

Bult, Peter

Dispersion of high oxygen permeability ionomers in water-propanol solutions

There is a growing interest in high oxygen permeability ionomers (HOPI) for better-performing proton exchange membrane fuel cell (PEMFC) catalyst layers. In this study, we used small-angle x-ray scattering (SAXS) to analyze dispersions of two types of perfluorinated sulfonic acid (PFSA) ionomers and a HOPI in water and propanol solvents, at concentrations between 1 wt% and 15 wt%. HOPI dispersions exhibited the interference peak typical of ionomers; by separately fitting the peak and higher- q regions with several models, we demonstrated that HOPI aggregates have a closer average spacing than conventional PFSA ionomers, and smaller aggregate size when assuming a cylindrical geometry. By measuring conventional PFSA ionomers with two side chain lengths and several equivalent weights, we showed that these side chain parameters alone did not explain the differences in aggregate spacing or size. In addition, the pattern was present whether samples were prepared in a 50/50 water/propanol or a more propanol-rich mixture. As such, the structural differences of HOPI could be due to its different backbone monomer. A better understanding of the influence of the HOPI chemistry on dispersion properties could help explain the ink structure and drying characteristics of HOPI observed in prior work. Future study of ionomer-catalyst mixtures, such as measuring ionomer adsorption to carbon, would help elucidate the role of ionomer from ink formulation to the cast electrode.

Aquivion

Structural Characterization of the Platinum Nanoparticle Hydrogen-Evolving Catalyst Assembled on Photosystem I by Light-Driven Chemistry

Directed assembly of abiotic catalysts onto biological redox protein frameworks is of interest as an approach for the synthesis of biohybrid catalysts that combine features of both synthetic and biological materials. In this report, we provide a multiscale characterization of the platinum nanoparticle (NP) hydrogen-evolving catalysts that are assembled by light-driven reductive precipitation of platinum from an aqueous salt solution onto the photosystem I protein (PSI), isolated from cyanobacteria as trimeric PSI. The resulting PSI-NP assemblies were analyzed using a combination of X-ray energy-dispersive spectroscopy (XEDS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), small-angle X-ray scattering (SAXS), and high-energy X-ray scattering with atomic pair distribution function (PDF) analyses. The results show that the PSI-supported NPs are approximately 1.8 nm diameter disk-shaped particles that assemble at discrete sites with 145 Å separation. This separation is too large to be consistent with NP nucleation and growth at a site adjacent to the F B cofactor site. Instead, we suggest a mechanism for NP growth at hydrophobic sites on the PSI stromal surface. The NPs photoreductively assembled on the PSI stromal surface are found to be analogous to the nanostructures produced by successive cycles of atomic layer deposition (ALD) of platinum onto 40 nm porous anodic alumina oxide supports, although the mechanisms for nucleation appear to differ. In conclusion, this work establishes a foundation for the investigation of the reductive assembly of abiotic metal catalysts at sites connected to photochemically reducing equivalent production in PSI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Structural mechanisms for binding and activation of a contact-quenched fluorophore by RhoBAST

The fluorescent light-up aptamer RhoBAST, which binds and activates the fluorophore–quencher conjugate tetramethylrhodamine-dinitroaniline with high affinity, super high brightness, remarkable photostability, and fast exchange kinetics, exhibits excellent performance in super-resolution RNA imaging. Here we determine the co-crystal structure of RhoBAST in complex with tetramethylrhodamine-dinitroaniline to elucidate the molecular basis for ligand binding and fluorescence activation. The structure exhibits an asymmetric “A”-like architecture for RhoBAST with a semi-open binding pocket harboring the xanthene of tetramethylrhodamine at the tip, while the dinitroaniline quencher stacks over the phenyl of tetramethylrhodamine instead of being fully released. Molecular dynamics simulations show highly heterogeneous conformational ensembles with the contact-but-unstacked fluorophore–quencher conformation for both free and bound tetramethylrhodamine-dinitroaniline being predominant. The simulations also show that, upon RNA binding, the fraction of xanthene-dinitroaniline stacked conformation significantly decreases in free tetramethylrhodamine-dinitroaniline. This highlights the importance of releasing dinitroaniline from xanthene tetramethylrhodamine to unquench the RhoBAST–tetramethylrhodamine-dinitroaniline complex. Using SAXS and ITC, we characterized the magnesium dependency of the folding and binding mode of RhoBAST in solution and indicated its strong structural robustness. The structures and binding modes of relevant fluorescent light-up aptamers are compared, providing mechanistic insights for rational design and optimization of this important fluorescent light-up aptamer-ligand system.

59 BASIC BIOLOGICAL SCIENCES

Formation of Non-Doped Cubic Lithium Lanthanum Zirconium Oxide Nanofibers: Insights from In Situ Synchrotron X-Ray Scattering

This study investigates the formation mechanism of non-doped cubic lithium lanthanum zirconium oxide (c-LLZO) nanofibers using in situ synchrotron X-ray scattering techniques. Electrospun polymer precursor nanofibers were annealed at temperatures up to 800 °C, enabling real-time tracking of phase transitions via simultaneous small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and evolved CO 2 gas analysis. The results reveal a three-step transformation pathway: polymer decomposition, formation of La 2 Zr 2 O 7 (LZO), and direct conversion of LZO to c-LLZO without intermediate tetragonal phases detected within the sensitivity of our in situ WAXS measurement. Cryo-electron energy loss spectroscopy (EELS) further elucidates the role of lithium diffusion, showing Li enrichment at fiber surfaces and Li deficiency in the interior, which stabilizes the cubic phase. This Li segregation effect in nanostructured LLZO materials extends beyond the previously reported size effect. This work advances the understanding of c-LLZO formation mechanisms and provides practical insights for optimizing synthesis routes to achieve phase-pure c-LLZO for solid-state battery applications.

LLZO phase stability

Effect of Thermodynamic and Environmental Factors on Crystallization of DNA‐Origami Superlattices

The directed self‐assembly of nanoscale materials into ordered superlattices presents a powerful strategy for creating next‐generation materials with programmable mechanical, optical, and photonic properties. Deoxyribonucleic acid (DNA) origami has emerged as a versatile scaffold for encoding nanoscale geometry and guiding the crystallization of complex 3D architectures. However, a systematic understanding of the parameters that govern the efficiency and quality of superlattice formation remains limited. In this study, we utilize octahedral DNA nanoscale frames as a model system to investigate the relative influence of key factors, including buffer composition, ionic strength, frame concentration, and thermal annealing protocols, on the size, order, and reproducibility of the resulting superlattices. Our findings provide a quantitative framework to rationally optimize DNA‐based assembly pathways. Structural characterization via small‐angle x‐ray scattering (SAXS), scanning electron microscopy (SEM), and optical microscopy validates the quality and fidelity of the assembled lattices. Moreover, by templating these DNA frameworks into inorganic replicas, we establish general design principles that extend beyond biomolecular systems, providing a foundation for the synthesis of programmable materials in broader nanofabrication contexts.

77 NANOSCIENCE AND NANOTECHNOLOGY

Discharge Rate‐Driven Li 2 O 2 Growth Exhibits Unconventional Morphology Trends in Solid‐State Li‐O 2 Batteries

Solid-state lithium oxygen batteries (LOBs) are known for their enhanced safety, higher electrochemical stability, and improved energy density compared to liquid-state LOBs. However, the investigation of solid-state LOBs is limited with little understanding of their discharge and charge processes. In this work, a polymer-based solid-state LOB is used to investigate the effect of discharge rate on lithium peroxide (Li 2 O 2 ) formation, the oxygen evolution reaction (OER), and cycle performance. Notably, we observe a counterintuitive trend: Li 2 O 2 particle size increases with increasing discharge current density, in contrast to liquid systems. This behavior arises from inherent space charge layers that restrict Li⁺ transport under high current, and spatially heterogeneous active sites at the solid electrolyte–cathode interface, directly evidenced by small angle X-ray scattering (SAXS), which govern nucleation accessibility and promote site-selective Li 2 O 2 growth. Furthermore, higher current densities improve ORR and OER efficiency but accelerate anode degradation, while lower currents promote side reactions. These opposing effects result in a trade-off that defines an optimal discharge rate (0.1 mA cm -2 ) for maximizing cycle life. This study provides a new mechanistic perspective on discharge-driven processes in solid-state LOBs and offers practical guidelines for performance optimization in future high-energy battery systems.

Discharge current density

Extrusion‐Based Printing of Nanostructured Fatty Acid Gels Incorporated in Hydrogels

Soft materials with unique nanostructures such as lamellar, hexagonal, and cubic morphologies can replicate complex structures that have potential in various fields, including biomedical and industrial applications. However, a key challenge in advancing the broader applications of 3D printing for these nanostructured soft materials is insufficient mechanical properties that hinder their printability and compromise structural stability in the final product. In this study, the suitability of a fatty acid‐based lamellar gel is evaluated for direct extrusion‐based 3D printing. Here, the lamellar gel with varying water content is integrated with a photocurable hydrogel to preserve the shape and stability of the final prints. Complex 2D and 3D design patterns are used to assess extrusion behavior, structural stability, and print precision under varying pressures. Small‐angle X‐ray Scattering (SAXS) measurements reveal the formation of lamellar nanostructures and confirm their retention after photocuring in various gels. Rheological analysis confirms that these gels exhibit key properties suitable for extrusion‐based 3D printing, such as shear‐thinning behavior. Additionally, tensile testing is conducted to evaluate the mechanical properties across cured print samples. This study underscores the potential of nanostructured gels as a robust and versatile platform, facilitating the development of materials engineered for various applications.

36 MATERIALS SCIENCE