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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 973 records · Page 54
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Extracorporeal membrane oxygenation promotes long chain fatty acid oxidation in the immature swine heart in vivo

Extracorporeal membrane oxygenation (ECMO) supports infants and children with severe cardiopulmonary compromise. Nutritional support for these children includes provision of medium- and long-chain fatty acids (FAs). However, ECMO induces a stress response, which could limit the capacity for FA oxidation. Metabolic impairment could induce new or exacerbate existing myocardial dysfunction. Using a clinically relevant piglet model, we tested the hypothesis that ECMO maintains the myocardial capacity for FA oxidation and preserves myocardial energy state. Provision of 13-Carbon labeled medium-chain FA (octanoate), longchain free FAs (LCFAs), and lactate into systemic circulation showed that ECMO promoted relative increases in myocardial LCFA oxidation while inhibiting lactate oxidation. Loading of these labeled substrates at high dose into the left coronary artery demonstrated metabolic flexibility as the heart preferentially oxidized octanoate. ECMO preserved this octanoate metabolic response, but also promoted LCFA oxidation and inhibited lactate utilization. Rapid upregulation of pyruvate dehydrogenase kinase-4 (PDK4) protein appeared to participate in this metabolic shift during ECMO. ECMO also increased relative flux from lactate to alanine further supporting the role for pyruvate dehydrogenase inhibition by PDK4. High dose substrate loading during ECMO also elevated the myocardial energy state indexed by phosphocreatine to ATP ratio. ECMO promotes LCFA oxidation in immature hearts, while maintaining myocardial energy state. These data support the appropriateness of FA provision during ECMO support for the immature heart.

clear magnetic resonance↗
DOE OSTI2023

Energetic electron transport in magnetic fields with island chains and stochastic regions

This paper investigates energetic electron transport in magnetized toroidal plasmas with magnetic fields characterized by island chains and regions of stochastic field lines produced by coil perturbations. We report on experiments performed in the DIII-D tokamak, which utilize electron cyclotron heating and current drive pulses to ‘tag’ electron populations within different locations across the discharge. The cross-field transport of these populations is then inferred from electron cyclotron emission measurements and gamma emission signals from scintillator detectors. Two types of energetic particles are distinguished and discussed: non-relativistic suprathermal electrons and relativistic runaway electrons. The magnetic field topology in each discharge is reconstructed with field-line tracing codes, which are also used to determine the location and scale of magnetic islands and stochastic regions. Comparison of simulations and experiments suggests that suprathermal transport is suppressed when the tagging is performed at a smaller radial location than the location of the $q = 1$ island chain and enhanced otherwise. Here q is the safety factor. We further demonstrate that increasing the width of the stochastic region within the edge plasma yields enhancement of the suprathermal electron transport.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Photoemission electron microscopy and scanning electron microscopy of Magnetospirillum magnetotacticum ’s magnetosome chains

Magnetotactic bacteria are of great interdisciplinary interest, since a vast field of applications from magnetic recording media to medical nanorobots is conceivable. A key feature for a further understanding is the detailed knowledge about the magnetosome chain within the bacteria. We report on two preparation procedures suitable for UHV experiments in reflective geometry. Further, we present the results of scanning electron microscopy, as well as the first photoemission electron microscopy experiments, both accessing the magnetosomes within intact magnetotactic bacteria and compare these to scanning electron microscopy data from the literature. From the images, we can clearly identify individual magnetosomes within their chains.

Keutner, Christoph↗
DOE OSTI2020

Rapid and Simultaneous Characterization of Drug Conjugation in Heavy and Light Chains of a Monoclonal Antibody Revealed by High-Resolution Ion Mobility Separations in SLIM

Antibody-drug conjugates (ADCs) have recently gained traction in the biomedical community due to their promise for human therapeutics and an alternative to chemotherapy for cancer. Crucial metrics for ADC efficacy, safety, and selectivity are their drug-antibody ratios (DARs). However, DAR characterization (i.e., determining the average number of conjugated drugs on the antibody) through analytical methods remains challenging due to the heterogeneity of drug conjugation as well as the numerous post-translational modifications possible in the monoclonal antibody. In this work, we report on the use of high-resolution ion mobility spectrometry separations in our structures for lossless ion manipulations coupled to mass spectrometry (SLIM IMS-MS) platform for the rapid and simultaneous characterization of the drug load profile (i.e., stoichiometric distribution of the number of conjugated drugs present on the mAb), determination of the weighted average DAR in both the heavy and light chains of a model antibody-drug conjugate, and calculation of the overall DAR of the ADC. After chemical reduction of the ADC and a subsequent 31.5 meter SLIM IMS separation the various drug bound antibody species could be well resolved for both chains. Furthermore, we also show that higher resolution separations were possible with SLIM IMS as compared to ones performed on a commercially available (~1 meter) drift tube IMS-MS platform. Interestingly, additional gas-phase substructures become evident with longer path length SLIM IMS, potentially providing insight related to how drug conjugation may alter the structural properties of a monoclonal antibody and thus affect its overall potency and/or selectivity for a given antigen. We expect high-resolution SLIM IMS separations will augment the existing toolbox for ADC characterization, particularly for structural confirmation to enable the rapid optimization of DAR for a given ADC and thus better understand its potential toxicity and potency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Removal of the Side Chain at the Active-Site Serine by a Glycine Substitution Increases the Stability of a Wide Range of Serine β-Lactamases by Relieving Steric Strain

Serine β-lactamases are bacterial enzymes that hydrolyze β- lactam antibiotics. They utilize an active-site serine residue as a nucleophile, forming an acyl-enzyme intermediate during hydrolysis. Here, thermal denaturation experiments as well as X-ray crystallography were performed to test the effect of substitution of the catalytic serine with glycine on protein stability in serine β-lactamases. Six different enzymes comprising representatives from each of the three classes of serine β-lactamases were examined, including TEM-1, CTX-M- 14, and KPC-2 of class A, P99 of class C, and OXA-48 and OXA-163 of class D. For each enzyme, the wild type and a serine-to-glycine mutant were evaluated for stability. The glycine mutants all exhibited enhanced thermostability compared to that of the wild type. In contrast, alanine substitutions of the catalytic serine in TEM-1, OXA-48, and OXA-163 did not alter stability, suggesting removal of the Cβ atom is key to the stability increase associated with the glycine mutants. The X-ray crystal structures of P99 S64G, OXA-48 S70G and S70A, and OXA-163 S70G suggest that removal of the side chain of the catalytic serine releases steric strain to improve enzyme stability. In addition, analysis of the torsion angles at the nucleophile position indicates that the glycine mutants exhibit improved distance and angular parameters of the intrahelical hydrogen bond network compared to those of the wild-type enzymes, which is also consistent with increased stability. The increased stability of the mutants indicates that the enzyme pays a price in stability for the presence of a side chain at the catalytic serine position but that the cost is necessary in that removal of the serine drastically impairs function. Our findings support the stability-function hypothesis, which states that active-site residues are optimized for substrate binding and catalysis but that the requirements for catalysis are often not consistent with the requirements for optimal stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

RNA–Polymer Conjugates via Direct Incorporation of the Chain Transfer Agent and PET–RAFT Polymerization

Covalent conjugation of RNA with synthetic polymers has emerged as a powerful approach for creating bioconjugates with synergistically enhanced properties. However, conventional methods require solid-phase synthesis to preinstall functional groups in RNA, significantly limiting practical applications. Here, we present a novel approach for synthesizing RNA–polymer conjugates via direct incorporation of chain transfer agent (CTA) into RNA through acylation chemistry and reversible addition–fragmentation chain transfer (RAFT) polymerization. A CTA-functionalized acyl imidazole reagent was synthesized to facilitate direct and covalent modification of various RNAs by reacting with their 2′-hydroxyl groups. Subsequent RAFT polymerization using RNA–CTA as a macro-CTA enabled direct grafting-from RNA, yielding RNA conjugates with controlled molecular weight and low dispersity. Notably, this postsynthetic modification strategy was successfully extended to modify biomass RNA, yielding thermoresponsive conjugates and biodegradable hydrogels. Overall, this advance allowed for the direct modification of synthetic and biomass RNAs, significantly enhancing the accessibility of functional RNA–polymer materials.

biomass↗
DOE OSTI2022

Accessing One-Dimensional Chains of Halogenoindates(III) in Organic–Inorganic Hybrids

Organic-inorganic hybrids of halogenoindates(III) are typically represented by one of the zero-dimensional units: InX 4 – , InX 5 2– , InX 6 3– , or In 2 X 11 5– . Higher dimensional anionic forms, although not forbidden, have remained almost elusive. Here, in this study, we report for the first time In 3+ -based organic–inorganic hybrids, (C 4 H 5 N 2 S) 2 InCl 5 and (C 4 H 5 N 2 S) 2 InBr 5 , with 1D anionic chains of trans-halide-bridged InX 6 octahedra whose formation is guided by 2-mercaptopyrimidinium cations (C 4 H 5 N 2 S + ). The chains are characterized by the significant ease of deformation, which is reflected in the elongation of the bridging bonds or the displacement of In 3+ ions. The materials show a robust band gap predominantly governed by C 4 H 5 N 2 S + cations. Dielectric relaxation processes in (C 4 H 5 N 2 S) 2 InBr 5 arise from the cations’ dynamics and suggest the ability of the brominated system to accommodate even larger cations. Our work represents a successful attempt to expand the structural diversity of halogenoindates(III) and opens a pathway to reach multifunctional 1D In 3+ -based hybrids.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Pressure-Induced Large Volume Collapse, Plane-to-Chain, Insulator to Metal Transition in CaMn 2 Bi 2

We report that in situ high pressure single crystal X-ray diffraction study reveals that the quantum material CaMn 2 Bi 2 undergoes a unique plane to chain structural transition between 2 and 3 GPa, accompanied by a large volume collapse. Puckered Mn–Mn honeycomb layer converts to quasi-one-dimensional (1D) zigzag chains above the phase transition pressure. Single crystal measurements reveal that the pressure-induced structural transformation is accompanied by a dramatic 2 orders of magnitude drop of resistivity. Although the ambient pressure phase displays semiconducting behavior at low temperatures, metallic temperature dependent resistivity is observed for the high pressure phase, as surprisingly, are two resistivity anomalies with opposite pressure dependences, while one of them could be a magnetic transition and the other originates from Fermi surface instability. Lastly, assessment of the total energies for hypothetical magnetic structures for high pressure CaMn 2 Bi 2 indicates that ferrimagnetism is thermodynamically favored.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Hygroscopicity of organic compounds as a function of carbon chain length, carboxyl, hydroperoxy, and carbonyl functional groups

The albedo and microphysical properties of clouds are controlled in part by the hygroscopicity of particles serving as cloud condensation nuclei (CCN). Hygroscopicity of complex organic mixtures in the atmosphere varies widely and remains challenging to predict. Here we present new measurements characterizing the CCN activity of pure compounds in which carbon chain length and the number of hydroperoxy, carboxyl, and carbonyl functional groups were systematically varied to establish the contributions of these groups to organic aerosol apparent hygroscopicity. Apparent hygroscopicity decreased with carbon chain length and increased with polar functional groups in the order carboxyl > hydroperoxy > carbonyl. Activation diameters at different supersaturations deviated from the -3/2 slope in log-log space predicted by Köhler theory, suggesting that water solubility limits CCN activity of particles composed of weakly functionalized organic compounds. Results are compared to a functional group contribution model that predicts CCN activity of organic compounds. The model performed well for most compounds but under-predicted the CCN activity of hydroperoxy groups. New best-fit hydroperoxy group/water interaction parameters were derived from the available CCN data. Lastly, these results may help improve estimates of the CCN activity of ambient organic aerosols from composition data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Atomistic Insights into Lithium–Glyme Solvate Ionic Liquids: Effects of Chain Length and Anion Coordination

For this study, mixtures of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in diglyme (G2), triglyme (G3) and tetraglyme (G4) at solvate ionic liquid (SIL) concentrations were investigated using classical molecular dynamics (cMD) simulations with a physically motivated force-field specifically developed for modeling these systems. The structural and dynamical properties of the mixtures were computed and analyzed. Lithium solvation shells, radial distribution functions, and X-ray structure factors were studied across the different SIL systems. Translational diffusion and rotational relaxation times were also evaluated, exhibiting similar trends with increasing glyme chain length. The results are consistent with experimental data and in good agreement with previous computational studies on G3 and G4. These findings validate the accuracy of the force field in modeling glyme systems and its use for describing the [Li(G2) 4/3 ][TFSI] mixture. Additionally, the thermal and electrochemical stability of these electrolytes were systematically examined. The thermal stability appears to be governed by cooperative interactions among glyme molecules, while the electrochemical stability is primarily influenced by Li + -anion interactions, which vary significantly with glyme chain length. Overall, the study sheds light on the crucial role of the anion in these glyme-based SILs and offers valuable insights into Li + -glyme systems at SIL concentrations, highlighting their promise as potential Li-ion battery electrolytes.

anions↗
DOE OSTI2017

Influence of Chain Rigidity and Dielectric Constant on the Glass Transition Temperature in Polymerized Ionic Liquids

Polymerized ionic liquids (PolyILs) are promising candidates for a wide range of technological applications due to their single ion conductivity and good mechanical properties. Tuning the glass transition temperature (T g ) in these materials constitutes a major strategy to improve room temperature conductivity while controlling their mechanical properties. In this paper, we show experimental and simulation results demonstrating that in these materials T g does not follow a universal scaling behavior with the volume of the structural units V m (including monomer and counterion). Instead, T g is significantly influenced by the chain flexibility and polymer dielectric constant. We propose a simplified empirical model that includes the electrostatic interactions and chain flexibility to describe T g in PolyILs. Finally, our model enables design of new functional PolyILs with the desired T g .

36 MATERIALS SCIENCE↗
DOE OSTI2021

AlCl 3 -Dosed Si(100)-2 × 1: Adsorbates, Chlorinated Al Chains, and Incorporated Al

The adsorption of AlCl 3 on Si(100) and the effect of annealing the AlCl 3 -dosed substrate were studied to reveal key surface processes for the development of atomic-precision, acceptor-doping techniques. This investigation was performed via scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. At room temperature, AlCl 3 readily adsorbed to the Si substrate dimers and dissociated to form a variety of species. Annealing the AlCl 3 -dosed substrate at temperatures below 450 °C produced unique chlorinated aluminum chains (CACs) elongated along the Si(100) dimer row direction. An atomic model for the chains is proposed with supporting DFT calculations. Al was incorporated into the Si substrate upon annealing at 450 °C and above, and Cl desorption was observed for temperatures beyond 450 °C. Al-incorporated samples were encapsulated in Si and characterized by secondary ion mass spectrometry (SIMS) depth profiling to quantify the Al atom concentration, which was found to be in excess of 10 20 cm –3 across a ~2.7 nm-thick δ-doped region. Here, the Al concentration achieved here and the processing parameters utilized promote AlCl 3 as a viable gaseous precursor for novel acceptor-doped Si materials and devices for quantum computing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Deprotonated Water Dimers: The Building Blocks of Segmented Water Chains on Rutile RuO2(110)

Despite the importance of RuO2 in photocatalytic water splitting and catalysis in general, the interactions of water with even its most stable (110) surface are not well-understood. In this study we employ a combination of high-resolution scanning tunneling microscopy imaging with density functional theory based ab initio molecular dynamics, and we follow the formation and binding of linear water clusters on coordinatively unsaturated ruthenium rows. We find that clusters of all sizes (dimers, trimers, tetramers, extended chains) are stabilized by donating one proton per every two water molecules to the surface bridge bonded oxygen sites, in contrast with water monomers that do not show a significant propensity for dissociation. The clusters with odd number of water molecules are less stable than the clusters with even number, and are generally not observed under thermal equilibrium. For all clusters with even numbers, the dissociated dimers represent the fundamental building blocks with strong intra-dimer hydrogen bonds and only very weak inter-dimer interactions resulting in segmented water chains.

ab initio molecular dynamics↗
DOE OSTI2016

Long-Chain Polysulfide Retention at the Cathode of Li–S Batteries

Lithium–sulfur batteries present a complex interconnected chemistry where the three components—anode, electrolyte, and cathode—strongly interact with each other. One of the main issues associated with these interactions is the dissolution in the electrolyte solution of part of the sulfur reduction products (mainly long-chain polysulfides) during the discharge reactions at the cathode. These dissolved species can migrate and react at the anode surface producing undesired insulating films. A potential solution to mitigate this problem is to resort to additional materials which can act as anchors of the soluble species thus avoiding their migration. Density functional theory and ab initio molecular dynamics simulations are employed to investigate the ability of certain substrates to retain long-chain polysulfides (Li 2 S 6 and Li 2 S 8 ) at their surfaces in the presence of a pure solvent or a lithiated solution. Nanopores of graphene are first tested because the cathode is usually a mix of sulfur and carbon. Then, MoS 2 and Mo-doped graphene are evaluated because of the well-known Mo–S affinity. Finally, a material which has been reported successful in experimental studies, MnO 2 , is analyzed and compared with another oxide surface, Fe 2 O 3 . Adsorption energies of the polysulfides to the surfaces and the detailed interactions of the Li ions and S atoms with the substrate are characterized via charge and geometric analyses. Both the Mo-containing materials and the oxides adsorb the polysulfides much more strongly than graphene nanopores do. However, some of these surfaces are found to be excessively reactive. Thus, a balance between affinity for S and moderate surface reactivity is found as a promising guideline for designing these materials.

25 ENERGY STORAGE↗
DOE OSTI2018

A Comparative Ab Initio Study of Anhydrous Dehydrogenation of Linear-Chain Alcohols on Cu(110)

The catalytic behavior of Cu surfaces in the anhydrous production of aldehydes from alcohols, a process of industrial significance, is puzzling: the two simplest alcohols (methanol and ethanol) show dramatically different decomposition behavior on Cu. In this work, we study the thermodynamic and kinetic processes involved in the anhydrous dehydrogenation of linear-chain alcohols including methanol, ethanol, 1-propanol, and 1-butanol on the Cu(110) surface using multiscale approaches. First, we obtain the adsorption structures and energies of the reaction intermediates, in which van der Waals (vdW) interactions play a crucial role. Then, we determine the kinetic barriers for the two dehydrogenation steps, namely, the O–H and the subsequent C–H bond-breaking on Cu. The reaction of methoxy-to-formaldehyde has a rather high-energy transition state, in contrast to that of alkoxide-to-aldehyde in the longer-chain systems. This difference qualitatively explains the lower production efficiency of formaldehyde on Cu. Finally, we simulate the production rates of aldehydes based on which we optimize reaction conditions and propose possible avenues for enhancing the production of anhydrous formaldehyde using Cu-based catalysts.

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

Long-Chain Lipids Facilitate Insertion of Large Nanoparticles into Membranes of Small Unilamellar Vesicles

Insertion of hydrophobic nanoparticles into phospholipid bilayers is limited to small particles that can incorporate into a hydrophobic membrane core between two lipid leaflets. Incorporation of nanoparticles above this size limit requires the development of challenging surface engineering methodologies. In principle, increasing the long-chain lipid component in the lipid mixture should facilitate incorporation of larger nanoparticles. Here, we explore the effect of incorporating very long phospholipids (C24:1) into small unilamellar vesicles on the membrane insertion efficiency of hydrophobic nanoparticles that are 5–11 nm in diameter. To this end, we improve an existing vesicle preparation protocol and utilized cryogenic electron microscopy imaging to examine the mode of interaction and evaluate the insertion efficiency of membrane-inserted nanoparticles. We also perform classical coarse-grained molecular dynamics simulations to identify changes in lipid membrane structural properties that may increase insertion efficiency. Furthermore, our results indicate that long-chain lipids increase the insertion efficiency by preferentially accumulating near membrane-inserted nanoparticles to reduce the thermodynamically unfavorable disruption of the membrane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Effects of Nanoparticle Morphology and Acyl Chain Length on Spontaneous Lipid Transfer Rates

In this paper, we report on studies of lipid transfer rates between different morphology nanoparticles and lipids with different length acyl chains. The lipid transfer rate of dimyristoylphosphatidylcholine (di-C 14 , DMPC) in discoidal “bicelles” (0.156 h –1 ) is 2 orders of magnitude greater than that of DMPC vesicles (ULVs) (1.1 × 10 –3 h –1 ). For both bicellar and ULV morphologies, increasing the acyl chain length by two carbons [going from di-C 14 DMPC to di-C 16 , dipalmitoylphosphatidylcholine (DPPC)] causes lipid transfer rates to decrease by more than 2 orders of magnitude. Results from small angle neutron scattering (SANS), differential scanning calorimetry (DSC), and fluorescence correlation spectroscopy (FCS) are in good agreement. Finally, the present studies highlight the importance of lipid dynamic processes taking place in different morphology biomimetic membranes.

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

Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications

Poly(ethylene oxide) (PEO)-based electrolytes have gained increasing attention in both the rechargeable battery industry and fundamental research, but any influence of the ions on the polymer conformation is not fully understood. Small-angle neutron scattering (SANS) is a powerful means to determine single-polymer chain conformations. We conducted SANS experiments on 50:50 blends of perdeuterated PEO (dPEO) and hydrogenous PEO (hPEO) of two different molecular weights (20 and 40 kDa) doped with two different salts (LiTFSI and LiClO 4 ) at various concentrations. An additional measurement with LiI is also reported. The scattering profiles of salt-doped dPEO/hPEO blends were measured, and the incoherent scattering from dPEO and hPEO doped with salt was measured separately. A strong low q upturn was observed in some of the blends and in the pure dPEO homopolymers. The statistical segment lengths of PEO–salt mixtures were derived using a Kratky analysis. The segment length decreases modestly with increasing amounts of LiTFSI but apparently first increases then decreases with added LiClO 4 . At the highest salt concentration examined (r = [Li+]/[EO] = 0.125), a roughly 10% decrease in the statistical segment length was observed in both LiTFSI and LiClO 4 -doped PEOs, for both molecular weights. This work confirms that added salt causes a contraction of the PEO chain dimensions, but the effect appears slightly weaker than reported recently. Certain difficulties in data analysis are also discussed, including the unexplained low q scattering even in pure deuterated polymers, uncertainties in background subtraction, and inappropriate application of the Debye function.

36 MATERIALS SCIENCE↗