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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Cylindrical C 96 Fullertubes: A Highly Active Metal-Free O 2 -Reduction Electrocatalyst

A new isolation protocol was recently reported for highly purified metallic Fullertubes D 5h -C 90 , D 3d -C 96 , and D 5d -C 100 , which exhibit unique electronic features. Here, we report the oxygen reduction electrocatalytic behavior of C 60 , C 70 (spheroidal fullerenes), and C 90 , C 96 , and C 100 (tubular fullerenes) using a combination of experimental and theoretical approaches. C 96 (a metal-free catalyst) displayed remarkable oxygen reduction reaction (ORR) activity, with an onset potential of 0.85 V and a halfway potential of 0.75 V, which are close to the state-of-the-art Pt/C benchmark catalyst values. Here we achieved an excellent power density of 0.75 W cm −2 using C 96 as a modified cathode in a proton-exchange membrane fuel cell, comparable to other recently reported efficient metal-free catalysts. Combined band structure (experimentally calculated) and free-energy (DFT) investigations show that both favorable energy-level alignment active catalytic sites on the carbon cage are responsible for the superior activity of C 96 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Disentangling the evolution of electrons and holes in photoexcited ZnO nanoparticles

The evolution of charge carriers in photoexcited room temperature ZnO nanoparticles in solution is investigated using ultrafast ultraviolet photoluminescence spectroscopy, ultrafast Zn K-edge absorption spectroscopy, and ab initio molecular dynamics (MD) simulations. The photoluminescence is excited at 4.66 eV, well above the band edge, and shows that electron cooling in the conduction band and exciton formation occur in <500 fs, in excellent agreement with theoretical predictions. The x-ray absorption measurements, obtained upon excitation close to the band edge at 3.49 eV, are sensitive to the migration and trapping of holes. They reveal that the 2 ps transient largely reproduces the previously reported transient obtained at 100 ps time delay in synchrotron studies. In addition, the x-ray absorption signal is found to rise in ∼1.4 ps, which we attribute to the diffusion of holes through the lattice prior to their trapping at singly charged oxygen vacancies. Indeed, the MD simulations show that impulsive trapping of holes induces an ultrafast expansion of the cage of Zn atoms in <200 fs, followed by an oscillatory response at a frequency of ∼100 cm−1, which corresponds to a phonon mode of the system involving the Zn sub-lattice.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Effect of Framework Composition and NH 3 on the Diffusion of Cu + in Cu-CHA Catalysts Predicted by Machine-Learning Accelerated Molecular Dynamics

Cu-exchanged zeolites rely on mobile solvated Cu + cations for their catalytic activity, but the role of the framework composition in transport is not fully understood. Ab initio molecular dynamics simulations can provide quantitative atomistic insight but are too computationally expensive to explore large length and time scales or diverse compositions. We report a machine-learning interatomic potential that accurately reproduces ab initio results and effectively generalizes to allow multinanosecond simulations of large supercells and diverse chemical compositions. Biased and unbiased simulations of [Cu(NH 3 ) 2 ] + mobility show that aluminum pairing in eight-membered rings accelerates local hopping and demonstrate that increased NH 3 concentration enhances long-range diffusion. The probability of finding two [Cu(NH 3 ) 2 ] + complexes in the same cage, which is key for SCR-NOx reaction, increases with Cu content and Al content but does not correlate with the long-range mobility of Cu + . Supporting experimental evidence was obtained from reactivity tests of Cu-CHA catalysts with a controlled chemical composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

An Ultra-microporous Metal-Organic Framework with Exceptional Xe Capacity

Molecular confinement plays a significant effect on trapped gas and solvent molecules. A fundamental understanding of gas adsorption within the porous confinement provides information necessary to design a material with improved selectivity. In this regard, metal organic frameworks (MOFs) adsorbents are ideal candidate materials to study confinement effects for weakly interacting gas molecules such as noble gases. Among the noble gases, Xenon (Xe) has practical applications in the medical, automotive and aerospace industries. In this communication, we report an ultra-microporous nickel-isonicotinate MOF with exceptional Xe uptake and selectivity compared to all benchmark MOF and porous organic cage materials. The selectivity arises because of the near perfect fit of the atomic Xe inside the porous confinement. Notably, at low partial pressure, the Ni-MOF interacts very strongly with Xe compared to the closely related Krypton gas (Kr) and more polarizable CO2. Further 129Xe NMR suggests a broad isotropic chemical shift due to the reduced motion as a result of confinement.

Confinement effects, atomically precise materials,↗
DOE OSTI2020

Intermolecular Coulombic Decay in Endohedral Fullerene at the 4 d → 4 f Resonance

Intermolecular processes offer unique decay mechanisms for complex systems to internally relax. Here, we report the observation of an intermolecular Coulombic decay channel in an endohedral fullerene, a holmium nitride complex (Ho 3 N) embedded within a C 80 fullerene, between neighboring holmium ions, and between the holmium complex and the carbon cage. By measuring the ions and the electrons in coincidence after XUV photoabsorption, we can isolate the different decay channels, which are found to be more prevalent relative to intra-atomic Auger decay.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Bond-centric modular design of protein assemblies

Directional interactions that generate regular coordination geometries are a powerful means of guiding molecular and colloidal self-assembly, but implementing such high-level interactions with proteins remains challenging due to their complex shapes and intricate interface properties. Here we describe a modular approach to protein nanomaterial design inspired by the rich chemical diversity that can be generated from the small number of atomic valencies. We design protein building blocks using deep learning-based generative tools, incorporating regular coordination geometries and tailorable bonding interactions that enable the assembly of diverse closed and open architectures guided by simple geometric principles. Experimental characterization confirms the successful formation of more than 20 multicomponent polyhedral protein cages, two-dimensional arrays and three-dimensional protein lattices, with a high (10%–50%) success rate and electron microscopy data closely matching the corresponding design models. Due to modularity, individual building blocks can assemble with different partners to generate distinct regular assemblies, resulting in an economy of parts and enabling the construction of reconfigurable networks for designer nanomaterials.

Biomaterials – proteins↗
DOE OSTI2025

Alpha-relaxation by scattering and medium-range atomic correlation in simple liquids

The relaxation dynamics of liquid and glass can be studied by inelastic x-ray or neutron scattering through the intermediate scattering function F(Q, t), where Q is the momentum transfer of scattering. Because of the time-consuming nature of these measurements, F(Q, t) is usually measured only at the first peak of the structure function S(Q), and its principal decay time is referred to as the α-relaxation time τ α . τ α is generally considered to describe the relaxation time of the bulk, which is related to viscosity and is controlled by the atomic cage around an atom. Here, through simulations on metallic liquids, we show that the α-relaxation time determined by scattering experiments does not purely reflect viscosity but is influenced by changes in spatial cooperativity. We also demonstrate that atomic caging is not exerted by the nearest neighbors but involves more cooperative atomic dynamics of the atomic medium-range order.

Glass transitions↗
DOE OSTI2020

Crossover from Rouse to Reptation Dynamics in Salt-Free Polyelectrolyte Complex Coacervates

Considerable interest in the dynamics and rheology of polyelectrolyte complex coacervates has been motivated by their industrial application as viscosity modifiers. A central question is the extent to which classical Rouse and reptation models can be applied to systems where electrostatic interactions play a critical role on the thermodynamics. By relying on molecular simulations, we present a direct analysis of the crossover from Rouse to reptation dynamics in salt-free complex coacervates as a function of chain length. This crossover shifts to shorter chain lengths as electrostatic interactions become stronger, which corresponds to the formation of denser coacervates. To distinguish the roles of Coulomb interactions and density, here we compare the dynamics of coacervates to those of neutral, semidilute solutions at the same density. Both systems exhibit a universal dynamical behavior in the connectivity-dominated (subdiffusion and normal diffusion) regimes, but the monomer relaxation time in coacervates is much longer and increases with increasing Bjerrum length. This is similar to the cage effect observed in glass-forming polymers, but the local dynamical slowdown is caused here by strong Coulomb attractions (ion pairing) between oppositely charged monomers. Our findings provide a microscopic framework for the quantitative understanding of coacervate dynamics and rheology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

In situ potassium and hydrogen ion exchange into a cubic zirconium silicate microporous material

The selective separation of ions from aqueous systems, and even in the human body, is a crucial to overall environmental management and health. Nanoporous materials are widely known for their selective removal of cations from aqueous media, and therefore have been targeted for use as a pharmaceutical to treat hyperkalemia. This study investigated the detailed crystallographic molecular mechanisms that control the potassium ion selectivity in the nanoporous cubic zirconium silicate (CZS) related materials. Using time-resolved in situ Raman spectroscopy and time-resolved in situ X-ray diffraction, the selectivity mechanisms were determined to involve a synchronous cation-cation repulsion process that serves to open a favorable coordination bonding environment for potassium, not unlike the ion selectivity filter process found in potassium ion channels in proteins. Enhancement of ion exchange was observed when the CZS material was in a partial protonated state (≈3:1 Na:H), causing an expansion of the unit-cell volume, enlargement of the 7 member-ring window, and distortion of framework polyhedra, which allowed increased accessibility to the cage structures and resulted in rapid irreversible potassium ion exchange.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Density functional study of the variants of inter-Coulombic decay resonances in the photoionization of Cl@C 60

Inter-Coulombic decay (ICD) resonances in the photoionization of Cl@C 60 endofullerene molecule are calculated using a perturbative density functional theory (DFT) method. This is the first ICD study of an open shell atom in a fullerene cage. Here, three classes of resonances are probed: (i) Cl inner vacancies decaying through C 60 outer continua, (ii) C 60 inner vacancies decaying through Cl outer continua, and (iii) inner vacancies of either system decaying through the continua of Cl-C 60 hybrid levels, the hybrid Auger-ICD resonances. Comparisons with Ar@C 60 results reveal that the properties of hybrid Auger-ICD resonances are affected by the extent of level hybridization.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Apolipoprotein A-I modulates HDL particle size in the absence of apolipoprotein A-II

Human high-density lipoproteins (HDLs) are a complex mixture of structurally related nanoparticles that perform distinct physiological functions. We previously showed that human HDL containing apolipoprotein A-I (APOA1) but not apolipoprotein A-II (APOA2), designated LpA-I, is composed primarily of two discretely sized populations. Here, we isolated these particles directly from human plasma by antibody affinity chromatography, separated them by high-resolution size-exclusion chromatography and performed a deep molecular characterization of each species. The large and small LpA-I populations were spherical with mean diameters of 109 Å and 91 Å, respectively. Unexpectedly, isotope dilution MS/MS with [ 15 N]-APOA1 in concert with quantitation of particle concentration by calibrated ion mobility analysis demonstrated that the large particles contained fewer APOA1 molecules than the small particles; the stoichiometries were 3.0 and 3.7 molecules of APOA1 per particle, respectively. MS/MS experiments showed that the protein cargo of large LpA-I particles was more diverse. Human HDL and isolated particles containing both APOA1 and APOA2 exhibit a much wider range and variation of particle sizes than LpA-I, indicating that APOA2 is likely the major contributor to HDL size heterogeneity. We propose a ratchet model based on the trefoil structure of APOA1 whereby the helical cage maintaining particle structure has two “settings”—large and small—that accounts for these findings. This understanding of the determinants of HDL particle size and protein cargo distribution serves as a basis for determining the roles of HDL subpopulations in metabolism and disease states.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Medium-Range Structural Order as the Driver of Activated Dynamics and Complexity Reduction in Glass-Forming Liquids

Here, we analyze in depth the Elastically Collective Nonlinear Langevin Equation theory of activated dynamics in metastable liquids to establish that the predicted inter-relationships between the alpha relaxation time, local cage and collective elastic barriers, dynamic localization length, and shear modulus are causally related within the theory to the medium range order (MRO) static correlation length. The latter grows exponentially with density for metastable hard sphere fluids and as a nonuniversal inverse power law with temperature for supercooled liquids under isobaric conditions. The physical origin of predicted connections between the alpha time and other metrics of cage order and the thermodynamic inverse dimensionless compressibility is fully established. It is discovered that although kinetic constraints from the real space first coordination shell are important for the alpha time, they are of secondary importance compared to the consequences of the more universal MRO correlations in both the modestly and deeply metastable regimes. This understanding sheds new light on the theoretical basis for, and prior successes of, the predictive mapping of chemically complex thermal liquids to effective hard sphere fluids based on matching their dimensionless compressibilities, a scheme we call “complexity reduction”. In essence, the latter is equivalent to the physical requirement that the thermal liquid MRO correlation equals that of its effective hard sphere analog. The mapping alone is shown to provide a remarkable level of quantitative predictive power for the glass transition temperature T g of 21 molecular and polymer liquids. Predictions for the chemically specific absolute magnitude and growth with cooling of the MRO correlation length are obtained and lie in the window of 2–6 nm at T g . Dynamic heterogeneity, elastic facilitation, and beyond pair structure issues are briefly discussed. Future opportunities to theoretically analyze the equilibrated deep glass regime are outlined.

cancer↗
DOE OSTI2020

Li-Metal Anode in Dilute Electrolyte LiFSI/TMP: Electrochemical Stability Using Ab Initio Molecular Dynamics

Ab initio molecular dynamics simulations were performed for Li + conducting electrolytes based on trimethyl phosphates (TMP) and lithium bis(fluorosulfonyl)imide (Li + FSI – ) salt in contact with a Li-metal electrode. We focused on the transient-state behavior at the electrolyte, interfacial electrolyte–Li-metal electrode, and lithium reference electrode–electrolyte–Li-metal electrode to study dynamics and activation energy barriers of the Li + ion, electrochemical and thermal stability of the interface electrode-electrolyte, and potential behavior of the Li-metal electrode, respectively. Our results show that in the most stable state, Li + ions are tetrahedrally coordinated to three TMPs and one FSI – . The inner solvation shell of a Li-ion is composed of three TMP and one FSI – in one contact ion-pair and four TMPs in a solvent-separated ion-pair. On the other hand, Li-ions transport through electrolyte cages takes place when they are coordinated with three or less molecules that could be a combination of TMPs and FSI – . The decomposition pathway of the LiFSI salt when in direct contact with the Li-metal anode starts with defluorination of FSI – , rapidly losing F– to the lithium surface, forming LiF species. The remaining FSO 2 NSO 2 –2 with the addition of 2e – from the Li-metal decomposes into SO 2 –2 and NFSO 2 –2 . SO 2 –2 deposits on the Li-surface and decomposes into Li 2 O and Li 2 S. The remaining NFSO 2 –2 defluorinates, losing F – ion to the lithium surface, resulting in LiF and the remaining NSO 2 –1 deposits on the lithium surface and decomposes in the following picoseconds, forming several binary compounds such as Li 3 N, Li 2 S and Li 2 O. In contrast, when the salt is solvated by the TMP molecules, avoiding a direct contact with the Li metal electrode, only one defluorination occurs, decomposing the FSI – into FSO 2 NSO 2 –2 and a F – . The two anions remain stable as they are solvated by the TMP molecules. Furthermore, we also analyzed the open circuit potential energy (OCPE) of the Li-metal electrode during the SEI formation. OCPE is calculated from the average local potential profile difference within the Li-metal electrode and a pristine Li-crystal reference electrode (LRE). When no SEI is formed, the Li-metal electrode has an average OCPE of +0.36 eV vs LRE. Due to the formation of a SEI, the Li-metal electrode has an average OCPE between -0.07 and -0.21 eV vs LRE. The OCPE of the Li-metal electrode decreases by ~0.42 eV when a SEI is formed.

25 ENERGY STORAGE↗
DOE OSTI2022

Subdiffusive High-Pressure Hydrogen Gas Dynamics in Elastomers

We report elastomeric rubber materials serve a vital role as sealing materials in the hydrogen storage and transport infrastructure. With applications including O-rings and hose liners, these components are exposed to pressurized hydrogen at a range of temperatures, cycling rates, and pressure extremes. High-pressure exposure and subsequent rapid decompression often lead to cavitation and stress-induced damage of the elastomer due to localization of the hydrogen gas. Here, we use all-atom classical molecular dynamics simulations to assess the impact of compositional variations on gas diffusion within the commonly used elastomer ethylene–propylene–diene monomer (EPDM). With the aim to build a predictive understanding of precursors to cavitation and to motivate material formulations that are less sensitive to hydrogen-induced failure, we perform systematic simulations of gas dynamics in EPDM as a function of temperature, gas concentration, and cross-link density. Our simulations reveal anomalous, subdiffusive hydrogen motion at pressure and intermediate times. We identify two groups of gas with different mobilities: one group exhibiting high mobility and one group exhibiting low mobility due to their motion being impeded by the polymer. With decreasing temperatures, the low-mobility group shows increased gas localization, the necessary precursor for cavitation damage in these materials. At lower temperatures, increasing cross-link density led to greater hydrogen gas mobility and a lower fraction of caged hydrogen, indicating that increasing cross-link density may reduce precursors to cavitation. Finally, we use a two-state kinetic model to determine the energetics associated with transitions between these two mobility states.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Tuning the Conformations of an M4L4 Cage and Their Impact on Catalysis

Enzymes catalyze chemical reactions with remarkable rate enhancements and selectivity. Supramolecular catalysis seeks to understand and emulate these outcomes, leveraging noncovalent interactions, electric fields, and controlled active site microenvironments to enhance catalysis in an enzyme-like fashion. The effects of conformational dynamics on supramolecular catalysts and assemblies are, however, relatively unexplored, despite their crucial role in enzyme rate enhancement. Here, we elucidate the conformational landscape of a model M4L4 supramolecular host through a rational approach: stabilizing a high-energy conformer through distal ligand modification and a transient intermediate state through symmetry-matched guest encapsulation, as well as tuning the conformer distribution through same-charge metal exchange at the host vertices. Each of these structural modifications induces a substantial shift in the host's conformational landscape, offering insights into the rational design of conformationally dynamic cages and enzymes. Although the thermodynamic properties of the dynamic Ga4L412- cage can be influenced by temperature, solvent, and guest binding, we find that conformational change occurs on a time scale that renders it rate-limiting in a model catalytic reaction, precluding rate enhancement through conformational selection. This concept is illustrated by locking the catalytically inactive conformer to a high-energy conformer that is catalytically competent. These findings demonstrate that precise modulation of the conformational landscape of supramolecular hosts provides an effective strategy for controlling their catalytic activity and binding.

Catalysis↗
DOE OSTI2025

An evolutionarily conserved tryptophan cage promotes folding of the extended RNA recognition motif in the hnRNPR ‐like protein family

Abstract The heterogeneous nuclear ribonucleoprotein (hnRNP) R‐like family is a class of RNA binding proteins in the hnRNP superfamily with diverse functions in RNA processing. Here, we present the 1.90 Å X‐ray crystal structure and solution NMR studies of the first RNA recognition motif (RRM) of human hnRNPR. We find that this domain adopts an extended RRM (eRRM1) featuring a canonical RRM with a structured N‐terminal extension (N ext ) motif that docks against the RRM and extends the β‐sheet surface. The adjoining loop is structured and forms a tryptophan cage motif to position the N ext motif for docking to the RRM. Combining mutagenesis, solution NMR spectroscopy, and thermal denaturation studies, we evaluate the importance of residues in the N ext –RRM interface and adjoining loop on eRRM folding and conformational dynamics. We find that these sites are essential for protein solubility, conformational ordering, and thermal stability. Consistent with their importance, mutations in the N ext –RRM interface and loop are associated with several cancers in a survey of somatic mutations in cancer studies. Sequence and structure comparison of the human hnRNPR eRRM1 to experimentally verified and predicted hnRNPR‐like proteins reveals conserved features in the eRRM.

Biochemistry & Molecular Biology↗
DOE OSTI2022

Coarse-Grained Simulations for the Characterization and Optimization of Hybrid Protein–DNA Nanostructures

We present here the combination of experimental and computational modeling tools for the design and characterization of protein–DNA hybrid nanostructures. Our work incorporates several features in the design of these nanostructures: (1) modeling of the protein–DNA linker identity and length; (2) optimizing the design of protein–DNA cages to account for mechanical stresses; (3) probing the incorporation efficiency of protein–DNA conjugates into DNA nanostructures. The modeling tools were experimentally validated using structural characterization methods like cryo-TEM and AFM. Our method can be used for fitting low-resolution electron density maps when structural insights cannot be deciphered from experiments, as well as enable in-silico validation of nanostructured systems before their experimental realization. Finally, these tools will facilitate the design of complex hybrid protein–DNA nanostructures that seamlessly integrate the two different biomolecules.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Elucidating the Impact of Cis – Trans Organic Structure Directing Agent Isomer Ratios on the Aluminum Distribution Within SSZ-39

Despite their widespread use, the mechanisms governing the synthesis of zeolite catalysts are still poorly understood. A notable example of this problem is the uncertainty surrounding the influence of synthesis conditions on the placement of Al atoms in the zeolite framework which determines the active sites available for catalytic species. In this work, the role of the cis to trans isomer ratio of the OSDA N,N-dimethyl-3-5-dimethylpiperidinium on the energetics of 26 distinct Al pair distributions in SSZ-39 is examined both in the presence and absence of Na using density functional theory calculations. The initial orientation of the OSDA was found to have a significant impact on the final energies present, necessitating the screening of a large number of initial orientations with force field calculations and single point DFT calculations. Ground state energies were found to vary significantly with the ratio of cis to trans OSDAs with a Boltzmann distribution revealing the most likely Al pair distributions shift from sharing the same 8 membered rings to sharing the same double six membered rings to having no shared subunits as one increases the amount of cis OSDA present within the framework. The presence of Na was found to favor Al pair distributions where both Als occupied the same 6-membered ring. When an implicit solvent model was used to evaluate ground state energies the ideal Na sites shifted from 6-membered rings to empty SSZ-39 cages while OSDA positions and orientations remained largely the same. To provide insight on how kinetic factors may influence Al distributions, formation energies we calculated for connected double six membered rings. Further, these formation energies revealed a preference for Al pairs to occupy the same 4-membered ring which indicates kinetic and thermodynamic control may lead to different Al distributions in SSZ-39.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗