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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 1,765 records · Page 98
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Abraham Szöke [Abraham Szoke - Physics Today Obituary]

Abraham Szöke, who did groundbreaking work in quantum optics, laser fusion, high-energy-density (HED) physics, and x-ray crystallography, died from complications of lymphoma on 26 January 2017. Born in Budapest, Hungary, on 1 December 1929, Szöke was an excellent student in mathematics and science who placed near the top of the famous Eötvös mathematics competition. He survived the Holocaust, and in 1949 he escaped from Communist Hungary and emigrated to Israel. He earned his doctorate in physics, with Saul Meiboom and William Low as his advisers, in 1962 from the Hebrew University of Jerusalem. As part of his thesis, he made the first measurement demonstrating the effect of radiation damping on nuclear magnetic resonance and its relation to transient maser action; that effect had been predicted a few years earlier by Nicolaas Bloembergen and Robert Pound.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Global shape mimicry of tRNA within a viral internal ribosome entry site mediates translational reading frame selection

The dicistrovirus intergenic region internal ribosome entry site (IRES) adopts a triple-pseudoknotted RNA structure and occupies the core ribosomal E, P, and A sites to directly recruit the ribosome and initiate translation at a non-AUG codon. A subset of dicistrovirus IRESs directs translation in the 0 and +1 frames to produce the viral structural proteins and a +1 overlapping open reading frame called ORFx, respectively. Here we show that specific mutations of two unpaired adenosines located at the core of the three-helical junction of the honey bee dicistrovirus Israeli acute paralysis virus (IAPV) IRES PKI domain can uncouple 0 and +1 frame translation, suggesting that the structure adopts distinct conformations that contribute to 0 or +1 frame translation. Using a reconstituted translation system, we show that ribosomes assembled on mutant IRESs that direct exclusive 0 or +1 frame translation lack reading frame fidelity. Finally, a nuclear magnetic resonance/small-angle X-ray scattering hybrid approach reveals that the PKI domain of the IAPV IRES adopts an RNA structure that resembles a complete tRNA. Here, the tRNA shape-mimicry enables the viral IRES to gain access to the ribosome tRNA-binding sites and form intermolecular contacts with the ribosome that are necessary for initiating IRES translation in a specific reading frame.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2013

Structure of the Type IVa Major Pilin from the Electrically Conductive Bacterial Nanowires of Geobacter sulfurreducens

Several species of bacteria are capable of reducing insoluble metal oxides as well as other extracellular electron acceptors. These bacteria play a critical role in the cycling of minerals in subsurface environments, sediments, and groundwater. In some species of bacteria, such as Geobacter sulfurreducens, the transport of electrons is facilitated by filamentous fibers that are referred to as bacterial nanowires. These nanowires belong to the type IVa family of pilin proteins and are mainly comprised of one subunit protein, PilA. Here, we report the high resolution solution nuclear magnetic resonance (NMR) structure of the PilA protein from G. sulfurreducens determined in detergent micelles. The protein is over 85% α-helical and exhibits similar architecture to the N-terminal regions of other non-conductive type IVa pilins. The detergent micelle interacts with the first 21 amino acids of the protein, indicating that this region likely associates with the bacterial inner membrane prior to fiber formation. A model of the G. sulfurreducens pilus fiber is proposed based on docking of this structure into the fiber model of the type IVa pilin from Neisseria gonorrhoeae. This model provides insight into the organization of aromatic amino acids that are important for electrical conduction.

bacterial nanowire↗
DOE OSTI2014

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package

A summary of the technical advances that are incorporated in the fourth major release of the Q-Chem quantum chemistry program is provided, covering approximately the last seven years. These include developments in density functional theory methods and algorithms, nuclear magnetic resonance (NMR) property evaluation, coupled cluster and perturbation theories, methods for electronically excited and open-shell species, tools for treating extended environments, algorithms for walking on potential surfaces, analysis tools, energy and electron transfer modelling, parallel computing capabilities, and graphical user interfaces. In addition, a selection of example case studies that illustrate these capabilities is given. These include extensive benchmarks of the comparative accuracy of modern density functionals for bonded and non-bonded interactions, tests of attenuated second order Møller-Plesset (MP2) methods for intermolecular interactions, a variety of parallel performance benchmarks, and tests of the accuracy of implicit solvation models. Finally, some specific chemical examples include calculations on the strongly correlated Cr 2 dimer, exploring zeolite-catalysed ethane dehydrogenation, energy decomposition analysis of a charged ter-molecular complex arising from glycerol photoionisation, and natural transition orbitals for a Frenkel exciton state in a nine-unit model of a self-assembling nanotube.

computational modelling↗
DOE OSTI2017

Quantitative Determination of Wax Contamination in Polystyrene HIPE Foam Using Solid-State NMR

Differences in molecular mobility between polystyrene foam and Brij-78 wax results in vast differences in the 1 H nuclear magnetic resonance (NMR) linewidth. This allows for the convenient determination of wax content in the polystyrene foam components of inertial confinement fusion targets via solid-state NMR. Lastly, contamination levels as low as 0.1% are easily recognized and quantified, and the detection limit is calculated to be 0.02% even when only 32 transients are recorded.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Conformational heterogeneity in closed and open states of the KcsA potassium channel in lipid bicelles

The process of ion channel gating—opening and closing—involves local and global structural changes in the channel in response to external stimuli. Conformational changes depend on the energetic landscape that underlies the transition between closed and open states, which plays a key role in ion channel gating. For the prokaryotic, pH-gated potassium channel KcsA, closed and open states have been extensively studied using structural and functional methods, but the dynamics within each of these functional states as well as the transition between them is not as well understood. In this study, we used solution nuclear magnetic resonance (NMR) spectroscopy to investigate the conformational transitions within specific functional states of KcsA. We incorporated KcsA channels into lipid bicelles and stabilized them into a closed state by using either phosphatidylcholine lipids, known to favor the closed channel, or mutations designed to trap the channel shut by disulfide cross-linking. A distinct state, consistent with an open channel, was uncovered by the addition of cardiolipin lipids. Using selective amino acid labeling at locations within the channel that are known to move during gating, we observed at least two different slowly interconverting conformational states for both closed and open channels. The pH dependence of these conformations and the predictable disruptions to this dependence observed in mutant channels with altered pH sensing highlight the importance of conformational heterogeneity for KcsA gating.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2023

Structure of amorphous materials in the NASICON system Na 1+x Ti 2 Si x P 3−x O 12

Abstract The structure of glasses in the sodium (Na) super-ionic conductor (NASICON) system Na 1 + x Ti 2 Si x P 3 − x O 12 with x = 0.8 and x = 1.0 was explored by combining neutron and high-energy x-ray diffraction with 29 Si, 31 P and 23 Na solid-state nuclear magnetic resonance (NMR) spectroscopy. The 29 Si magic angle spinning (MAS) NMR spectra reveal that the silica component remains fully polymerized in the form of Si 4 units, i.e. the silicon atoms are bound to four bridging oxygen atoms. The 31 P{ 23 Na} rotational echo adiabatic passage double resonance (REAPDOR) NMR data suggest that the 31 P MAS NMR line shape originates from four-coordinated P n units, where n = 1, 2 or 3 is the number of bridging oxygen atoms per phosphorus atom. These sites differ in their 31 P- 23 Na dipolar coupling strengths. The results support an intermediate range order scenario of a phosphosilicate mixed network-former glass in which the phosphate groups selectively attract the Na + modifier ions. Titanium takes a sub-octahedral coordination environment with a mean Ti–O coordination number of 5.17(4) for x = 0.8 and 4.86(4) for x = 1.0. A mismatch between the P–O and Si–O bond lengths of 8% is likely to inhibit the incorporation of silicon into the phosphorus sites of the NASICON crystal structure.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Hyperfine splitting of the 2s 1/2 and 2p 1/2 levels in lithium-like Pr 56+

Measurements of hyperfine splittings in highly charged ions are sensitive to details of the nuclear structure and the nuclear magnetic field distribution, but the proper interpretation of the measurements requires that the atomic structure is understood in sufficient detail. Lastly, we discuss the reasoning behind various recent experiments and what advantage is offered by the study of the Li-like ion of a mid-Z element such as praseodymium.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2017

Anisotropy of Spin Fluctuations in a Tetragonal Heavy Fermion Antiferromagnet CeRhAl 4 Si 2

An antiferromagnetic (AFM) Kondo lattice compound CeRhAl 4 Si 2 , which exhibits successive AFM transitions at T N1 =14 K and T N2 =9 K in zero external field, has been microscopically investigated by means of 27 Al nuclear magnetic resonance (NMR) technique. In the high temperature range, magnetic excitations of 4f electrons can be well explained by isotropic localized spin fluctuations. Below ~50 K, it begins to show a characteristic anisotropy of spin fluctuations, which suggests a competition between spin fluctuations and nesting instability in this system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Uncertainty analysis of Raman spectra for measuring ortho-parahydrogen compositions

Determining ortho-parahydrogen compositions at cryogenic temperatures is an important quality control for liquid hydrogen custody exchange. High orthohydrogen compositions lead to an exothermic reaction resulting in increased boil off and increased venting losses of liquid hydrogen product by either the supplier or consumer. Traditional methods for measuring ortho-parahydrogen compositions such as hot-wire anemometry, nuclear magnetic resonance, and infrared spectroscopy are typically inconvenient at best. As the number of cryogenic hydrogen systems continue to increase, there is an increased need for flexible, standardized techniques for post processing composition measurements. A Raman spectrometer implemented in the Cryo-Catalysis Hydrogen Experimental Facility (CHEF) has demonstrated incredible flexibility for composition measurements of cryogenic hydrogen flows through a wide range of temperatures and pressures with the Raman probe in-situ at cryogenic temperatures. This article analyzes the uncertainty of Raman spectroscopy data of cryogenic hydrogen equilibrated at temperatures in IONEX catalyst. Spectra from hydrogen catalyzed to the equilibrium ortho-parahydrogen composition are processed and compared to expected statistical distributions for method verification.

08 HYDROGEN↗
DOE OSTI2021

CeNTREX: a new search for time-reversal symmetry violation in the 205 Tl nucleus

The Cold molecule Nuclear Time-Reversal EXperiment (CeNTREX) is a new effort aiming for a significant increase in sensitivity over the best present upper bounds on the strength of hadronic time reversal (T) violating fundamental interactions. The experimental signature will be shifts in nuclear magnetic resonance frequencies of 205 Tl in electrically-polarized thallium fluoride (TlF) molecules. Here we describe the motivation for studying these T-violating interactions and for using TlF to do so. To achieve higher sensitivity than earlier searches for T-violation in TlF, CeNTREX uses a cryogenic molecular beam source, optical state preparation and detection, and modern methods of coherent quantum state manipulation. Details of the measurement scheme and the current state of the apparatus are presented, with quantitative measurements of the TlF beam. Lastly, the estimated sensitivity and methods to control systematic errors are discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Disentangling cation effects on ion mobility and structure in ionic liquid electrolytes

Ionic liquids (ILs) are low-temperature molten salts, where ion transport is primarily governed by ion–ion interactions. Yet, the impact of organic IL cations on critical electrolyte properties such as ion dissociation and overall transport behavior in lithium-salt-doped ILs remains poorly understood. Moreover, despite their critical role in designing IL-based electrolytes for energy storage applications, ion–ion interactions and ion-specific transport under an applied electrical potential are seldom quantified, largely due to the unique experimental and computational challenges involved. Herein, we compare transport properties obtained using 1 H, 7 Li, and 19 F pulsed-field gradient nuclear magnetic resonance (NMR) and electrophoretic NMR (eNMR) with those measured by electrochemical impedance spectroscopy. Non-equilibrium molecular dynamics (MD) simulations and eNMR confirm the presence of negatively charged [Li(TFSI) n ] (1−n) aggregates that migrate towards the positive electrode, resulting in negative lithium transference numbers. Equilibrium MD simulations reveal a vehicular Li ion transport mechanism facilitated by long-lived aggregates with Li + cations strongly bound to multiple TFSI − anions. Finally, we observe an inverse relationship between the apparent charge of the TFSI − anion in the neat IL, which is dictated by the IL cation, and Li + transport in the salt-doped systems. This highlights the opportunity to tune electrolyte performance by tailoring cation chemistry.

Li-ion batteries↗
DOE OSTI2018

Gaining insight into the $T\,_2^*$– T 2 relationship in surface NMR free-induction decay measurements

One of the primary shortcomings of the surface nuclear magnetic resonance (NMR) freeinduction decay (FID) measurement is the uncertainty surrounding which mechanism controls the signal’s time dependence. Ideally, the FID-estimated relaxation time T$*\atop{2}$ that describes the signal’s decay carries an intimate link to the geometry of the pore space. In this limit the parameter T$*\atop{2}$ is closely linked to a related parameter T 2 , which is more closely linked to pore-geometry. If T$*\atop{2}$ T 2 the FID can provide valuable insight into relative pore-size and can be used to make quantitative permeability estimates. However, given only FID measurements it is difficult to determine whether T$*\atop{2}$ is linked to pore geometry or whether it has been strongly influenced by background magnetic field inhomogeneity. If the link between an observed T$*\atop{2}$ and the underlying T 2 could be further constrained the utility of the standard surface NMR FID measurement would be greatly improved. We hypothesize that an approach employing an updated surface NMR forward model that solves the full Bloch equations with appropriately weighted relaxation terms can be used to help constrain the T$*\atop{2}$ –T 2 relationship. Weighting the relaxation terms requires estimating the poorly constrained parameters T 2 and T 1 ; to deal with this uncertainty we propose to conduct a parameter search involving multiple inversions that employ a suite of forward models each describing a distinct but plausible T$*\atop{2}$ –T 2 relationship. We hypothesize that forward models given poor T 2 estimates will produce poor data fits when using the complex-inversion, while forward models given reliable T 2 estimates will produce satisfactory data fits. By examining the data fits produced by the suite of plausible forward models, the likely T$*\atop{2}$ –T 2 can be constrained by identifying the range of T 2 estimates that produce reliable data fits. Synthetic and field results are presented to investigate the feasibility of the proposed technique.

58 GEOSCIENCES↗
DOE OSTI2018

Reliable noise measure in time-gated NMR data

Time gating is a commonly used approach in the pre-processing of nuclear magnetic resonance data before inversion. Gating suppresses spurious signals that can degrade recovered decay time distributions and therefore often stabilizes inversion. However, care must be taken in applying this technique when assumptions of uncorrelated Gaussianity break down and reduce stacking efficiency. If not properly accounted for, unreliable noise estimates introduce inversion artefacts through over- or underfitting of the data. Block-bootstrap resampling of noise realization proxies obtained through data phasing can be used to generate reliable noise estimates for the windows. Benefits of the approach are demonstrated through inversion of synthetic and borehole data. Finally, analysis confirms that bootstrapped noise metrics are more reliable under variable noise conditions and result in more stable inversion results.

58 GEOSCIENCES↗
DOE OSTI2019

Estimating T2 from surface NMR FID data using a forward model based on the full-Bloch equation

An integral component of the surface nuclear magnetic resonance forward model involves predicting the magnitude of the transverse magnetization following excitation. To predict the transverse magnetization, the Bloch equation must be solved. Traditional surface NMR forward models solve a simplified version of the Bloch equation where the relaxation terms are neglected. A shortcoming of this approach is that it can struggle to accurately describe the impact of relaxation during pulse effects. To address this concern, an alternative forward model based on solution of the full-Bloch equation is proposed. The advantage of the proposed scheme is that it implicitly accounts for relaxation during pulse effects, increases the flexibility to implement alternative parametrizations of the inverse model, and can readily describe an arbitrary excitation protocol given that it no longer requires closed form expressions of the transverse magnetizations. To demonstrate the potential of the updated forward modelling scheme, a novel approach for the inversion of complex-valued free-induction decay (FID) data is presented. The inverse model is reparametrized in order to produce depth profiles of the water content, T2* and T2. This approach has great potential to enhance the ability of FID measurements to provide insights into pore size and permeability as it can provide direct sensitivity to T2. In contrast, traditional approaches that employ a forward model based on the simplified Bloch equation and estimate only T2* are plagued by uncertainty surrounding the link between T2* and pore size/permeability. Synthetic and field results are presented to demonstrate the feasibility of the proposed forward model and FID inversion framework.

58 GEOSCIENCES↗
DOE OSTI2023

Involvement of the Streptococcus mutans PgfE and GalE 4-epimerases in protein glycosylation, carbon metabolism, and cell division

Streptococcus mutans is a key pathogen associated with dental caries and is often implicated in infective endocarditis. This organism forms robust biofilms on tooth surfaces and can use collagen-binding proteins (CBPs) to efficiently colonize collagenous substrates, including dentin and heart valves. One of the best characterized CBPs of S. mutans is Cnm, which contributes to adhesion and invasion of oral epithelial and heart endothelial cells. These virulence properties were subsequently linked to post-translational modification (PTM) of the Cnm threonine-rich repeat region by the Pgf glycosylation machinery, which consists of 4 enzymes: PgfS, PgfM1, PgfE, and PgfM2. Inactivation of the S. mutans pgf genes leads to decreased collagen binding, reduced invasion of human coronary artery endothelial cells, and attenuated virulence in the Galleria mellonella invertebrate model. The present study aimed to better understand Cnm glycosylation and characterize the predicted 4-epimerase, PgfE. Using a truncated Cnm variant containing only 2 threonine-rich repeats, mass spectrometric analysis revealed extensive glycosylation with HexNAc2. Compositional analysis, complemented with lectin blotting, identified the HexNAc2 moieties as GlcNAc and GalNAc. Comparison of PgfE with the other S. mutans 4-epimerase GalE through structural modeling, nuclear magnetic resonance, and capillary electrophoresis demonstrated that GalE is a UDP-Glc-4-epimerase, while PgfE is a GlcNAc-4-epimerase. While PgfE exclusively participates in protein O-glycosylation, we found that GalE affects galactose metabolism and cell division. Furthermore, this study further emphasizes the importance of O-linked protein glycosylation and carbohydrate metabolism in S. mutans and identifies the PTM modifications of the key CBP, Cnm.

4-epimerases↗
DOE OSTI2022

Elucidation of complex respiratory chains: a straightforward strategy to monitor electron transfer between cytochromes

Abstract Cytochromes are electron transfer (ET) proteins essential in various biological systems, playing crucial roles in the respiratory chains of bacteria. These proteins are particularly abundant in electrogenic microorganisms and are responsible for the efficient delivery of electrons to the cells’ exterior. The capability of sending electrons outside the cells open new avenues to be explored for emerging biotechnological applications in bioremediation, microbial electrosynthesis, and bioenergy fields. To develop these applications, it is critical to identify the different redox partners and to elucidate the stepwise ET along the respiratory paths. However, investigating direct ET events between proteins with identical features in nearly all spectroscopic techniques is extremely challenging. Nuclear magnetic resonance (NMR) spectroscopy offers the possibility to overcome this difficulty by analysing the alterations of the spectral signatures of each protein caused by electron exchange events. The uncrowded NMR spectral regions containing the heme resonances of the cytochromes display unique and distinct signatures in the reduced and oxidized states, which can be explored to monitor ET within the redox complex. In this study, we present a strategy for a fast and straightforward monitorization of ET between c-type cytochromes, using as model a triheme periplasmic cytochrome and a membrane-associated monoheme cytochrome from the electrogenic bacterium Geobacter sulfurreducens. The comparison between the 1D 1H NMR spectra obtained for samples containing the two cytochromes and for samples containing the individual proteins clearly demonstrated a unidirectional ET within the redox complex. This strategy provides a simple and straightforward means to elucidate complex biologic respiratory ET chains.

Morgado, Leonor (ORCID:0000000237605180)↗
DOE OSTI2023

The structure of the high-affinity nickel-binding site in the Ni,Zn-HypA•UreE2 complex

Abstract The maturation pathway for the nickel-dependent enzyme urease utilizes the protein UreE as a metallochaperone to supply Ni(II) ions. In Helicobacter pylori urease maturation also requires HypA and HypB, accessory proteins that are commonly associated with hydrogenase maturation. Herein we report on the characterization of a protein complex formed between HypA and the UreE2 dimer. Nuclear magnetic resonance (NMR) coupled with molecular modelling show that the protein complex apo, Zn-HypA•UreE2, forms between the rigorously conserved Met-His-Glu (MHE motif) Ni-binding N-terminal sequence of HypA and the two conserved His102A and His102B located at the dimer interface of UreE2. This complex forms in the absence of Ni(II) and is supported by extensive protein contacts that include the use of the C-terminal sequences of UreE2 to form additional strands of β-sheet with the Ni-binding domain of HypA. The Ni-binding properties of apo, Zn-HypA•UreE2 and the component proteins were investigated by isothermal titration calorimetry using a global fitting strategy that included all of the relevant equilibria, and show that the Ni,Zn-HypA•UreE2 complex contains a single Ni(II)-binding site with a sub-nanomolar KD. The structural features of this novel Ni(II) site were elucidated using proteins produced with specifically deuterated amino acids, protein point mutations, and the analyses of X-ray absorption spectroscopy, hyperfine shifted NMR features, as well as molecular modeling coupled with quantum-mechanical calculations. The results show that the complex contains a six-coordinate, high-spin Ni(II) site with ligands provided by both component proteins.

Zambelli, Barbara (ORCID:0000000238760051)↗