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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 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Communication: Molecular gears

The {sup 1}H nuclear magnetic resonance spectrum of hexamethylbenzene orientationally ordered in the nematic liquid crystal ZLI-1132 is analysed using covariance matrix adaptation evolution strategy. The spectrum contains over 350 000 lines with many overlapping transitions, from which four independent direct dipolar couplings are obtained. The rotations of the six methyl groups appear to be correlated due to mutual steric hindrance. Adjacent methyl groups show counter-rotating or geared motion. Hexamethylbenzene thus behaves as a molecular hexagonal gear.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

A novel method to predict internal relative humidity in cementitious materials by 1H NMR

In sealed cementitious materials, the internal relative humidity (RH) decrease is mainly due to the water activity depression caused by menisci formation in partially-saturated pores. This process can be conveniently described with the evolution of the Kelvin radius. To obtain the Kelvin radius, a novel method based on the evolution of pore volumes quantified by {sup 1}H nuclear magnetic resonance (NMR) and mercury intrusion porosimetry (MIP) was developed. This approach was validated against experimental results for cementitious materials with a range of water to cement ratios from 0.30 to 0.46. A comparison between the Kelvin radius calculated with this approach with a previously published method using data obtained from MIP and chemical shrinkage was presented. A sensitivity analysis for the new prediction method was performed using a bootstrapping technique.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Effect of electrochemical cycling on microstructures of nanocomposite silicon electrodes using hyperpolarized 129 Xe and 7 Li NMR spectroscopy

The microstructural stability of composite electrodes during electrochemical cycling is critically important as it dictates the performance of Li-ion batteries. The issue becomes even more important for the high capacity alloying anode such as silicon that typically exhibits dramatic lithiation–delithiation-induced volume changes. The solid electrolyte interphase (SEI) layer formed on the active electrode surface has a profound effect on the overall microstructural stability of composite electrodes. An ideal SEI layer allows Li+ ions in and out of the electrode, but is an insulator to electrons, preventing the electrolyte from being further reduced. However, the SEI layers formed during initial lithiation may experience changes or degradation with subsequent cycling, adversely affecting the electrode performance. A combination of hyperpolarized 129 Xe and 7 Li nuclear magnetic resonance spectroscopies was applied to probe the microstructures of nanocomposite silicon electrodes at various stages of the lithiation–delithiation cycle. The results obtained from this study shed light on the degradation mechanism of nanocomposite Si electrodes upon electrochemical cycling and should prove useful in the effort to design more robust electrodes in the future.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Porous structure and mechanical strength of cement-lime pastes during setting

The acceleration of a cement paste setting as a result of lime addition may be shown from isothermal calorimetry measurements. We investigated the underlying mechanisms through two techniques that provide information on porous structure (using Nuclear Magnetic Resonance) and mechanical properties (elastic modulus measured by rheometry). The correlation of the two sets of results on a cement paste clearly reveals the successive steps of setting, and particularly highlights the so-called induction period. We show that this induction period disappears in the presence of lime, leading to an acceleration of the setting. We also show that beyond some critical concentration of added lime the acceleration of setting is negligible.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Investigations of CuFeS{sub 2} semiconductor mineral from ocean rift hydrothermal vent fields by Cu NMR in a local field

The results of investigating natural samples of chalcopyrite mineral CuFeS{sub 2} from massive oceanic sulfide ores of the Mid-Atlantic ridge by the {sup 63}Cu nuclear magnetic resonance (NMR {sup 63}Cu) in a local field at room temperature are presented. The significant width of the resonance lines found in the {sup 63}Cu NMR spectrum directly testifies to a wide distribution of local magnetic and electric fields in the investigated chalcopyrite samples. This distribution can be the consequence of an appreciable deviation of the structure of the investigated chalcopyrite samples from the stoichiometric one. The obtained results show that the pulsed {sup 63}Cu NMR can be an efficient method for studying the physical properties of deep-water polymetallic sulfides of the World Ocean.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Effect of carbonate and phosphate ratios on the transformation of calcium orthophosphates

Graphical abstract: Complexes among phosphate, carbonate and calcium have been prepared via a facile hydrothermal route. The synthesized product at the low (0.15) and the high (1.8) molar ratio of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} is calcium phosphate hydrate and hydroxylapatite (HAp), respectively. Molar ratios of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} are effective on the reduction of carbonate activity during the crystallization of HAp. - Highlights: • Formation of different complexes from CO{sub 3}{sup 2−}, PO{sub 4}{sup 3−} and Ca{sup 2+} solutions at 60 °C. • Molar ratios of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2} cause changes in phase and size of synthesized products. • Addition of PO{sub 4}{sup 3} inhibited the activity of CO{sub 3}{sup 2−} during bound with Ca{sup 2+}. • The phase transformation was completed, when CO{sub 3}{sup 2−} peaks disappeared in FTIR. • PO{sub 4}{sup 3−}, CO{sub 3}{sup 2−} and Ca{sup 2+} distributed heterogeneously on the surface of precipitation. - Abstract: Complexes among phosphate, carbonate and calcium have been synthesized by a designed hydrothermal method. Effects of carbonate and phosphate ratios on the transformation of calcium-orthophosphates were investigated. With X-ray diffraction measurement the synthesized product at the low (0.15) and the high (1.8) molar ratio of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} is calcium phosphate hydrate at pH 9.0, and hydroxylapatite (HAp) at pH 8.0, respectively. Fourier transform infrared spectroscopy of product at the high ratio (1.8) of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} shows that the CO{sub 3}{sup 2−} peaks disappear, and the strong peaks at 1412 and 1460 cm{sup −1} are assigned to the vibrations of PO{sub 4}{sup 3−} in HAp. {sup 31}P nuclear magnetic resonance spectra of products at the low (0.15–0.6) to the high (1.2–1.8) ratios of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} are obtained at 2.9 and 2.7 ppm, respectively. Molar ratios of PO{sub 4}{sup 3−}/CO{sub 3}{sup 2−} are effective on the reduction of carbonate activity during the formation and infiltration events of calcium-phosphate surface precipitates, and are subsequently enclosed during HAp formation.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Effect of carboxylic acid of periodic mesoporous organosilicas on the fructose-to-5-hydroxymethylfurfural conversion in dimethylsulfoxide systems

This manuscript presents the preparation and catalytic application of highly ordered benzene bridged periodic mesoporous organosilicas (PMOs) functionalized with carboxylic acid (–COOH) group at varied density. The COOH-functionalized PMOs were synthesized by one-step condensation of 1,4-bis (triethoxysilyl) benzene and carboxylic group containing organosilane carboxyethylsilanetriol sodium salt using Brij-76 as the template. The obtained materials were characterized by a mean of methods including powder X-ray diffraction, nitrogen adsorption-desorption, scanning- and transmission electron microscopy, and {sup 13}C solid-state nuclear magnetic resonance measurements. The potentials of the obtained PMO materials with ordered mesopores were examined as solid catalysts for the chemical conversion of fructose to 5-hydroxymethylfurfural (HMF) in an organic solvent. The results showed that COOH-functionalized PMO with 10% COOH loading exhibited best results for the fructose to HMF conversion and selectivity. The high surface area, the adequate density acid functional group, and the strength of the PMO materials contributing to a promising catalytic ability were observed.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Structural Origins of High MoO 3 Solubility in Peraluminous Borosilicate Glasses

Molybdenum (Mo) imposes strict loading limits in conventional borosilicate nuclear waste glasses due to the tendency of tetrahedral molybdate [MoO 4 ] 2− species to phase-separate and crystallize as alkali molybdates. Here, we demonstrate an unprecedented 13.96 wt % (7.51 mol %) MoO 3 solubility in peraluminous sodium aluminoborosilicate glasses a ∼15× increase over their peralkaline counterparts. Using Raman spectroscopy, multinuclear and dipolarcorrelation magic angle spinning nuclear magnetic resonance (MAS NMR), electron paramagnetic resonance (EPR), and scanning transmission electron microscopy (STEM)-energy dispersive spectroscopy (EDS), we reveal that Nadeficient, low optical basicity conditions stabilize octahedral MoO 6 units, which polymerize into molybdite-like Mo−O clusters dispersed within the glass matrix. These Mo-rich clusters suppress the formation of depolymerized [MoO 4 ] 2− environments typically responsible for Na 2 MoO 4 precipitation and instead promote the formation of Na 2 Mo 2 O 7 as the saturation phase. Concurrently, Mo solubility drives the conversion of AlO 4 − to higher-coordination AlO 5 species, liberating Na + that is subsequently sequestered in molybdate-rich domains. The combined evolution of Mo coordination, modifier redistribution, and network depolymerization provides a mechanistic basis for the markedly enhanced Mo solubility in peraluminous compositions. These findings establish new structural guidelines for designing aluminoborosilicate waste forms with substantially greater capacity to incorporate Mo-rich nuclear waste streams.

Amorphous materials↗
DOE OSTI2015

Transcription factor genes essential for cell proliferation and replicative lifespan in budding yeast

Many of the lifespan-related genes have been identified in eukaryotes ranging from the yeast to human. However, there is limited information available on the longevity genes that are essential for cell proliferation. Here, we investigated whether the essential genes encoding DNA-binding transcription factors modulated the replicative lifespan of Saccharomyces cerevisiae. Heterozygous diploid knockout strains for FHL1, RAP1, REB1, and MCM1 genes showed significantly short lifespan. {sup 1}H-nuclear magnetic resonance analysis indicated a characteristic metabolic profile in the Δfhl1/FHL1 mutant. These results strongly suggest that FHL1 regulates the transcription of lifespan related metabolic genes. Thus, heterozygous knockout strains could be the potential materials for discovering further novel lifespan genes. - Highlights: • Involvement of yeast TF genes essential for cell growth in lifespan was evaluated. • The essential TF genes, FHL1, RAP1, REB1, and MCM1, regulate replicative lifespan. • Heterozygous deletion of FHL1 changes cellular metabolism related to lifespan.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

Note: Spin-exchange optical pumping in a van

The advent of spin-hyperpolarization techniques designed to overcome the sensitivity issue of nuclear magnetic resonance owing to polarization transfer from more ordered systems has recently raised great enthusiasm. However, the out-of-equilibrium character of the polarization requires a close proximity between the area of production and the site of use. We present here a mobile spin-exchange optical pumping setup that enables production of laser-polarized noble gases in a standalone mode, in close proximity to hospitals or research laboratories. Only compressed air and mains power need to be supplied by the host laboratory.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2017

Synthesis of Biodegradable and Blood-Compatible Polyurethane Based on Poly(vinylpyrrolidone)

Three kinds of degradable and blood-compatible polyurethane (PU) were synthesized by coupling hydroxyl-terminated poly(vinylpyrrolidone) (PVP) with diisocyanate-terminated PU. The chemical structure and molecular weight of the synthesized copolymer were systematically characterized by nuclear magnetic resonance spectrum ({sup 1}HNMR), Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The hydrophilicity and water absorption of the synthesized PU was increased by introducing PVP segment. To evaluate the hemocompatibility and degradability of the modified PU films, the extent of platelet adsorption, plasma recalcification time, hemolysis and degradation were measured. All results indicated that the blood compatibility and degradability of the PU films were improved significantly after introduction PVP segment into PU.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Abnormal difference between the mobilities of left- and right-twisted conformations of C{sub 6}H{sub 12}N{sub 2} roto-symmetrical molecules at very low temperatures

We report an abnormal difference of low-temperature mobility of left-twisted and right-twisted conformations of roto symmetric molecules C{sub 6}H{sub 12}N{sub 2} (dabco) located in the same positions in crystal Zn{sub 2}(C{sub 8}H{sub 4}O{sub 4}){sub 2}⋅C{sub 6}H{sub 12}N{sub 2}. The difference between {sup 1}H NMR (Nuclear Magnetic Resonance) spin-relaxation data for left-twisted and right-twisted molecules reaches ∼3 × 10{sup 3} times at 8 K and tends to grow at lower temperatures. We argue that taking into account four-component relativistic Dirac wave functions in the vicinity of the nodal plane of dabco molecules and vacuum fluctuations due to virtual particle-antiparticle pairs can explain the changes which C{sub 6}H{sub 12}N{sub 2} conformations undergo at low temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Enhanced Mechanical and Barrier Performance of Poly (Lactic Acid) Based Nanocomposites Using Surface Acetylated Starch Nanocrystals

Poly (lactic) acid (PLA) based nanocomposites reinforced with starch nanocrystals (SNC) extracted from high amylopectin waxy maize starch and acetylated starch nanocrystals (Ac-SNC), were prepared and their influence on the overall properties of PLA nanocomposites were studied. The two nanofillers (SNC and Ac-SNC) were incorporated in PLA at two different loadings (1 and 3 wt%) by solvent casting and evaporation technique. Surface acetylation of SNC was confirmed by Fourier Transform infra-red spectroscopy and nuclear magnetic resonance spectroscopy and the crystalline structure by X-ray diffraction. This paper reports the influence of incorporating unacetylated and surface acetylated starch nanocrystals on morphological, barrier, mechanical, and rheological properties of PLA based nanocomposites. While both nanofillers improved the properties of PLA, the PLA-Ac-SNC had superior properties to that of PLA-SNC nanocomposites, due to better filler dispersion and interaction with the polymer matrix. These sustainable nanocomposites with improved properties will expand the application of these bio-sourced starch nanocrystals. Graphical Abstract: .

36 MATERIALS SCIENCE↗
DOE OSTI2013

Design, synthesis and evaluation of a potent substrate analog inhibitor identified by scanning Ala/Phe mutagenesis, mimicking substrate co-evolution, against multidrug-resistant HIV-1 protease

Highlights: •Inhibitors against MDR HIV-1 protease were designed, synthesized and evaluated. •Lead peptide (6a) showed potent inhibition (IC{sub 50}: 4.4 nM) of MDR HIV-1 protease. •(6a) Showed favorable binding isotherms against NL4-3 and MDR proteases. •(6a) Induced perturbations in the {sup 15}N-HSQC spectrum of MDR HIV-1 protease. •Molecular modeling suggested that (6a) may induce total flap closure inMDR protease. -- Abstract: Multidrug-resistant (MDR) clinical isolate-769, human immunodeficiency virus type-1 (HIV-1) protease (PDB ID: (1TW7)), was shown to exhibit wide-open flaps and an expanded active site cavity, causing loss of contacts with protease inhibitors. In the current study, the expanded active site cavity of MDR769 HIV-1 protease was screened with a series of peptide-inhibitors that were designed to mimic the natural substrate cleavage site, capsid/p2. Scanning Ala/Phe chemical mutagenesis approach was incorporated into the design of the peptide series to mimic the substrate co-evolution. Among the peptides synthesized and evaluated, a lead peptide (6a) with potent activity (IC{sub 50}: 4.4 nM) was identified against the MDR769 HIV-1 protease. Isothermal titration calorimetry data showed favorable binding profile for 6aagainst both wild type and MDR769 HIV-1 protease variants. Nuclear magnetic resonance spectrum of {sup 15}N-labeled MDR769 HIV-1 protease in complex with 6a showed some major perturbations in chemical shift, supporting the peptide induced conformational changes in protease. Modeling analysis revealed multiple contacts between 6a and MDR769 HIV-1 protease. The lead peptide-inhibitor, 6a, with high potency and good binding profile can be used as the basis for developing potent small molecule inhibitors against MDR variants of HIV.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

NMR shielding and spin–rotation constants of {sup 175}LuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br, {sup 127}I) molecules

This presentation demonstrates the relativistic effects on the spin-rotation constants, absolute nuclear magnetic resonance (NMR) shielding constants and shielding spans of {sup 175}LuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br, {sup 127}I) molecules. The results are obtained from calculations performed using density functional theory (non-relativistic and four-component relativistic) and coupled-cluster calculations. The spin-rotation constants are compared with available experimental values. In most of the molecules studied, relativistic effects make an order of magnitude difference on the NMR absolute shielding constants.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Phase transitions and potential ferroelectricity in noncentrosymmetric KNaNbOF 5

Increasing the number of known ferroelectrics requires expanding the chemical design space and mechanisms producing ferroelectricity. To that end, we examine the displacive, noncentrosymmetric-to-centrosymmetric phase transition in the oxyfluoride KNaNbOF 5 using ab initio calculations and Landau theory. Here we predict an intermediate Pnma phase occurs in the transition from the known low- and high-temperature phases, Pna2 1 and Cmcm, respectively, which we subsequently confirm using high-resolution and in situ 19 F magic-angle spinning nuclear magnetic resonance. Using the intermediate structure, we then calculate the monodomain polarization switching barrier in KNaNbOF 5 to be ~ 93 meV per formula unit, comparable to existing ferroelectrics. The reversal of the polarization is due to uncompensated antipolar displacements of oxygen and fluorine and does not require oxygen and fluorine site exchange as in other nonswitchable heteroanionic materials, which makes KNaNbOF 5 a viable oxyfluoride for a switchable electric polarization.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Kondo Physics and Unconventional Superconductivity in the U Intermetallic U 2 PtC 2 Revealed by NMR

The set of slides begins by discussing the topic NMR of heavy fermion superconductors under the topics heavy fermion materials, superconductivity, and nuclear magnetic resonance. The history of these phenomena is sketched, with particular mention made of CeCu 2 Si 2 , UPt 3 , and UBe 13 . Unconventional superconductivity, which is non-phonon mediated superconductivity, presents a high T c (up to ~150 K), and involves a more complicated spin/orbital wave function. The presentation then goes on to give experimental NMR results for U 2 PtC 2 and Pu-115’s.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

pH-dependent structural change of the extracellular sensor domain of the DraK histidine kinase from Streptomyces coelicolor

Highlights: ► We described the biochemical and biophysical properties of the extracellular sensory domain (ESD) of DraK histidine kinase. ► The ESD of DraK showed a reversible pH-dependent conformational change in a wide pH range. ► The E83 is an important residue for the pH-dependent conformational change. -- Abstract: Recently, the DraR/DraK (Sco3063/Sco3062) two-component system (TCS) of Streptomycescoelicolor has been reported to be involved in the differential regulation of antibiotic biosynthesis. However, it has not been shown that under which conditions and how the DraR/DraK TCS is activated to initiate the signal transduction process. Therefore, to understand the sensing mechanism, structural study of the sensory domain of DraK is highly required. Here, we report the biochemical and biophysical properties of the extracellular sensory domain (ESD) of DraK. We observed a reversible pH-dependent conformational change of the ESD in a pH range of 2.5–10. Size-exclusion chromatography and AUC (analytical ultracentrifugation) data indicated that the ESD is predominantly monomeric in solution and exists in equilibrium between monomer and dimer states in acidic condition. Using NMR (nuclear magnetic resonance) and CD (circular dichroism) spectroscopy, our findings suggest that the structure of the ESD at low pH is more structured than that at high pH. In particular, the glutamate at position 83 is an important residue for the pH-dependent conformational change. These results suggest that this pH-dependent conformational change of ESD may be involved in signal transduction process of DraR/DraK TCS.

60 APPLIED LIFE SCIENCES↗