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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 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Structural insights into Lewis acid- and F4TCNQ-doped conjugated polymers by solid-state magnetic resonance spectroscopy

Molecular doping strategies facilitate orders of magnitude enhancement in the charge carrier mobility of organic semiconductors (OSCs). Understanding the different doping mechanisms and molecular-level constraints on doping efficiency related to the material energy levels is crucial to develop versatile dopants for OSCs. Given the compositional and structural heterogeneities associated with OSC thin films, insight into dopant–polymer interactions by long-range techniques such as X-ray scattering and electron microscopy is exceedingly challenging to obtain. This study employs short-range probes, solid-state (ss)NMR and EPR spectroscopy, to resolve local structures and intermolecular interactions between dopants such as F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), Lewis acid BCF (tris[pentafluorophenyl] borane) and Lewis base conjugated polymer, PCPDTBT (P4) (poly[2,6-(4,4-bis(2-hexadecyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene)-alt-4,7(2,1,3-benzothiadiazole)]). Analysis of 1 H and 13 C ssNMR spectra of P4, P4 : F4TCNQ and P4 : BCF blends indicates that the addition of dopants induces local structural changes in the P4 polymer, and causes paramagnetism-induced signal broadening and intensity losses. The hyperfine interactions in P4 : BCF and P4 : F4TCNQ are characterized by two-dimensional pulsed EPR spectroscopy. For P4 : F4TCNQ, 19 F ssNMR analysis indicates that the F4TCNQ molecules are distributed and aggregated into different local chemical environments. By comparison, BCF molecules are intermixed with the P4 polymer and interact with traces of water molecules to form BCF–water complexes that serve as Brønsted acid sites, as revealed by 11 B ssNMR spectroscopy. These results indicate that the P4–dopant blends exhibit complex morphology with different distributions of dopants, whereby the combined use of ssNMR and EPR provides essential insights into how higher doping efficiency is observed with BCF and a mediocre efficiency is associated with F4TCNQ molecules.

36 MATERIALS SCIENCE↗
NASA NTRS1972

Molecular beam simulation of planetary atmospheric entry: Some recent results

Molecular beam sources for producing fast beams containing CO2 and atomic oxygen are discussed. Results pertinent to the design and calibration of mass spectrometer ion source for measurement of the Martian atmosphere during the free molecule portion of the entry trajectory are also presented. The shortcomings and advantages of the simulation technique are discussed. It is shown that an open cavity configuration retains sensitivity to atomic oxygen, provides reasonable signal enhancement from the stagnation effect, is not highly sensitive to pitch and yaw effects, and presents no unforeseen problems in measuring CO2 or atomic oxygen. The simulation techniques used provide assistance in designing, developing, and (potentially) in testing and calibrating the required flight instrument.

French, J. B.↗
NASA NTRS2012

Mass Spectrometric Studies of Oxides

Current studies at NASA Glenn on oxide thermodynamics are discussed. Previous studies on the vaporization of B2O3 in reducing atmospheres led to inconsistent studies when B was used as a reductant. It is shown that liquid B2O3 does not wet B and a clear phase separation was noted in the Knudsen cell. This problem was solved by using FeB and Fe2B to supply a different and constant activity of B. The thermodynamic data thus derived are compared to quantum chemical composite calculations. A major problem in high temperature mass spectrometry is the determination of accurate ionization cross sections, particularly for molecules. The method of Deutsch and Mark shows promise and some sample calculations are discussed. Finally current studies on the thermodynamics of rare earth silicates are discussed. Here the problems are obtaining a measurable signal from SiO2 vaporization and non-equilibrium vaporization. The use of a Ta reducing agent provides a stronger signal, which is related to silica activity. The Whitman-Motzfeld relation adapted to KEMS measurements is applied to obtain equilibrium pressures.

Jacobson, Nathan S.↗
DOE OSTI2021

Counting mRNA copies in intact bacterial cells by fluctuation localization imaging-based fluorescence in situ hybridization (fliFISH)

A method for measuring mRNA copies in intact bacterial cells by fluctuation localization imaging-based fluorescence in situ hybridization (fliFISH) is presented. Unlike conventional single molecule FISH, where the presence of a transcript is determined by fluorescence intensity, fliFISH relies on On-Off duty cycles of photo-switching dyes to set a predetermined threshold for distinguishing true signals from background noise. The method provides a quantitative approach for detecting and counting true mRNA copies and rejecting false signals with high accuracy.

Hu, Dehong↗
NASA NTRS1983

Infrared laser optogalvanic spectroscopy of molecules

Infrared laser optogalvanic spectra of portions of the NH3 nu3 band at 9.5 microns and the NO2 nu3 band at 6.2 microns have been recorded using CW tunable diode lasers to probe dc electrical discharges in pure NH3 and an NO2/He gas mixture. Two contributions to the optogalvanic signal are identified: one which corresponds to an increase in discharge impedance and is seen only for irradiation of the negative glow region; and a second which corresponds to a decrease in discharge impedance and is seen for irradiation of all other discharge regions and the volume outside the interelectrode region. Mechanisms by which infrared laser irradiation may cause impedance changes in the discharge are proposed.

Webster, C. R.↗
NASA NTRS1984

Absorption features in the 5-8 micron spectra of protostars

High signal-to-noise ratio spectra in the range of 5-8 microns of four sources embedded in molecular clouds are examined using low-temperature laboratory measurements of the 5-8-micron spectra of simple molecules and their mixtures. The absorption, apparent in all four sources, is characterized by highly distinct features ranging from two relatively narrow bands at 6.0 and 6.8 microns in W33A to a broad, shallow, and partially structured feature extending from 5.2 to 7.8 microns in Mon R2-IRS2, BN, and NGC2264. The first feature (W33A) is explained by the OH bending mode in H2O and the CH deformation modes in saturated hydrocarbons; while the second feature (Mon R2-IRS2-type) is explained by the presence of a mixture of saturated and unsaturated hydrocarbons possibly containing strongly electronegative groups.

Tielens, A. G. G. M.↗
DOE OSTI2021

Dynamic Nuclear Polarization Enhanced Nuclear Spin Optical Rotation

Here, nuclear spin optical rotation (NSOR) has been investigated as a magneto-optical effect, which holds the potential for applications, including hybrid optical-nuclear magnetic resonance (NMR) spectroscopy and gradientless imaging. The intrinsic nature of NSOR renders its detection relatively insensitive, which has prevented it moving from a proof of concept to a method supporting chemical characterizations. In this work, the dissolution dynamic nuclear polarization technique is introduced to provide nuclear spin polarization, increasing the signal-to-noise ratio by several thousand times. NSOR signals of 1 H and 19 F nuclei are observed in a single scan for diluted compounds, which has made this effect suitable for the determination of electronic transitions from a specific nucleus in a large molecule.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Optically Enhanced Solid-State 1 H NMR Spectroscopy

Low sensitivity is the primary limitation to extending nuclear magnetic resonance (NMR) techniques to more advanced chemical and structural studies. Photochemically induced dynamic nuclear polarization (photo-CIDNP) is an NMR hyperpolarization technique where light is used to excite a suitable donor–acceptor system, creating a spin-correlated radical pair whose evolution drives nuclear hyperpolarization. Systems that exhibit photo-CIDNP in solids are not common, and this effect has, up to now, only been observed for 13 C and 15 N nuclei. However, the low gyromagnetic ratio and natural abundance of these nuclei trap the local hyperpolarization in the vicinity of the chromophore and limit the utility for bulk hyperpolarization. Here, we report the first example of optically enhanced solid-state 1 H NMR spectroscopy in the high-field regime. This is achieved via photo-CIDNP of a donor–chromophore–acceptor molecule in a frozen solution at 0.3 T and 85 K, where spontaneous spin diffusion among the abundant strongly coupled 1 H nuclei relays polarization through the whole sample, yielding a 16-fold bulk 1 H signal enhancement under continuous laser irradiation at 450 nm. These findings enable a new strategy for hyperpolarized NMR beyond the current limits of conventional microwave-driven DNP.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Three mutations repurpose a plant karrikin receptor to a strigolactone receptor

Significance Parasitic plants like witchweed cause huge losses in crop yield in Africa. A key part to the success of witchweed is to start its life cycle upon sensing small molecules called strigolactones, which are exuded from roots of host plants into the soil. Witchweed sense host-derived strigolactones through receptors called HTLs. It is thought that the evolutionary origin of HTLs is a receptor called KAI2 in nonparasitic plants, which can respond to different small molecules such as karrikins. By making three changes in the protein sequence of KAI2, this hybrid receptor can now sense both strigolactones and karrikins. These results help in understanding how receptors can evolve to sense different signals and can lead to solutions for combating pesky witchweed.

Arellano-Saab, Amir↗
NASA NTRS1973

Recombination in radar meteors

Recombinations in the ionized columns generated by faint radar meteors are observed as: (1) A rapid loss of returned signal in the first few milliseconds after formation of the column; (2) an apparent absence of bright, low meteors; and (3) anomalies in apparent diffusion rates. Recombination at rates characteristic of dissociative recombination of ionized atmospheric molecules N2(+) and O2(+) is completely consistent with the observations. It appears either that the molecules are ionized in the initial formation of the ionized column or that there is rapid charge exchange. Recombination is a sufficient cause for the differences between diffusion measures and other atmospheric studies.

Southworth, R. B.↗
NASA NTRS1991

Analysis of volatiles present in interplanetary dust and stratospheric particles collected on large area collectors

Results are presented from an analysis of six chondritic interplanetary dust particles (IDPs) and 22 other stratospheric particles collected on large-area collector, carried out in order to obtain information on the nature, distribution, and form of volatiles in IDPs. A laser microprobe/mass spectrometer (LMMS) was used to extract volatile elements and molecules from particles larger than 10 microns, and an improved hexane rinsing technique was developed for the removal of contaminants. Results show that, because of contamination from silicone oil, freon, and hexane, most of the LMMS signal from IDPs can be interpreted as arising from contamination. Therefore, a species was not considered indigenous unless the signal was an order of magnitude greater in abundance than that released from a pure contaminant coated on gold.

Hartmetz, C. P.↗
NASA NTRS1986

Two-photon laser-induced fluorescence detection of OH

The TP-LIF OH sensor is based on the principle that a molecule having multiple energy states, all of which are bonding, can be pumped into the highest state with the resulting fluorescence being blue-shifted relative to all pumping wavelengths. In this way, one can successfully discriminate against virtually all noise sources in the system using long wavelength blocking filters in conjunction with solar-blind photomultiplier tubes. Thus, these systems tend to be signal limited rather than signal-to-noise limited as is true of the SP-LIF technique as well as other conventional analytical methods. The trick to achieving the above sampling scheme, with high efficiency, is in the use of high photon fluxes of short time duration. Obviously, the latter type of light source is fulfilled nicely by available pulsed lasers. From an operational point of view, however, this laser source needs to be tunable. The latter characteristic permits extremely high selectivity for the detection of a diatomic or simple polyatomic molecule by taking advantage of the high-resolution spectroscopic features of these type species.

Davis, D. D.↗
NASA NTRS1991

Observations of formaldehyde and search for cyanoacetylene in Comet Brorsen-Metcalf (1989o)

The Very Large Array (VLA) was used in September 1989 to search Comet P/Brorsen-Metcalf (1989o) for the 1 sub 11-1 sub 10 transition of formaldehyde (H2CO) at 4,829.659 MHz and for the J equals 1-0, F equals 2-1 rotational transition of cyanoacetylene (HC3N) at 9098.3321 MHz. A new technique was used in reducing the data. Data blocks which were either 3x3 pixels, 5x5 pixels, or 9x9 pixels were examined for a signal from H2CO. Using this approach, different pixel clusters within the field of view can be sampled to optimize the coupling of the synthesized beam to the gas distribution. HC3N is of immediate interest as a cometary molecule because it may be a reservoir of carbon and a source of cometary CN. Our search for HC3N emission at 3.3 cm wavelength demonstrated that for this molecule the VLA can be expected to reach significant levels of sensitivity in many comets.

Snyder, Lewis E.↗
NASA NTRS1992

Evidence for endohedral muonium in K(x) C60 and consequences for electronic structure

Positive muons injected into solid C60, K4C60, and K6C60 form vacuumlike muonium with a (6-12) percent probability. Observation of coherent spin precession of muonium establishes that all three materials are nonmagnetic and nonconducting at low temperatures. From the temperature dependence of the signals we estimate the electronic band gaps in K4C60 and K6C60 to be considerably smaller than in C60. The similarity of the muonium centers supports a model in which a muonium atom is caged inside the C60 molecule in pure C60 or the C60 exp -x molecular ion in K(x)C60.

Kiefl, R. F.↗
NASA NTRS2002

Biosensors for DNA sequence detection

DNA biosensors are being developed as alternatives to conventional DNA microarrays. These devices couple signal transduction directly to sequence recognition. Some of the most sensitive and functional technologies use fibre optics or electrochemical sensors in combination with DNA hybridization. In a shift from sequence recognition by hybridization, two emerging single-molecule techniques read sequence composition using zero-mode waveguides or electrical impedance in nanoscale pores.

Review↗
DOE OSTI2020

The Structural Basis of T4 Phage Lysis Control: DNA as the Signal for Lysis Inhibition

Optimal phage propagation depends on the regulation of the lysis of the infected host cell. In T4 phage infection, lysis occurs when the holin protein (T) forms lesions in the host membrane. However, the lethal function of T can be blocked by an antiholin (RI) during lysis inhibition (LIN). LIN sets if the infected cell undergoes superinfection, then the lysis is delayed until host/phage ratio becomes more favorable for the release of progeny. It has been thought that a signal derived from the superinfection is required to activate RI. Here we report structures that suggest a radically different model in which RI binds to T irrespective of superinfection, causing it to accumulate in a membrane as heterotetrameric 2RI–2T complex. Moreover, we show the complex binds non-specifically to DNA, suggesting that the gDNA from the superinfecting phage serves as the LIN signal and that stabilization of the complex by DNA binding is what defines LIN. Finally, we show that soluble domain of free RI crystallizes in a domain-swapped homotetramer, which likely works as a sink for RI molecules released from the RI–T complex to ensure efficient lysis. These results constitute the first structural basis and a new model not only for the historic LIN phenomenon but also for the temporal regulation of phage lysis in general.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Isolating solvent–solute hydrogen bonding interactions via 2D IR solvation shell spectroscopy

The solvation shell around a solute is a fundamental feature of liquid-phase solutions, determining the behavior and properties of both the solute and the overall solution. Direct experimental measurements of the solvation shell properties are challenging due to the strong signals generated from the bulk solvent, which overwhelm the small contribution of the solvation shell. Here, we use ultrafast two dimensional infrared (2D IR) spectroscopy and intermolecular cross-peaks to isolate the IR absorption spectrum of methanol molecules in the solvation shell surrounding the solute N-methylacetamide. We demonstrate that the intermolecular coupling between the solvent and solute vibrations is indirectly mediated by a low-frequency hydrogen-bonding mode, suggesting an important mechanism for anharmonic coupling induced by hydrogen bonds. From the relative frequency shifts and cross-peak anisotropy, we find that methanol molecules surrounding N-methylacetamide form stronger and distinctly oriented hydrogen bonds than those in the bulk solvent. Here, we also compare these results with the solvent spectra of the solute N,N-dimethylacetamide to investigate how solute structural changes alter the solvation shell and the contribution of N–H hydrogen bond donation. Our results are supported by molecular dynamics simulations, which provide detailed insights into the hydrogen-bonding distributions. Through these results, we demonstrate 2D solvation shell spectroscopy to be a valuable method for investigating solvation structures and dynamics without interference from the bulk solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Characterization of cellular oxidative stress response by stoichiometric redox proteomics

The thiol redox proteome refers to all proteins whose cysteine thiols are subjected to various redox-dependent posttranslational modifications (PTMs) including S-glutathionylation (SSG), S-nitrosylation (SNO), S-sulfenylation (SOH), and S-sulfhydration (SSH). These modifications can impact various aspects of protein function, including activity, binding, conformation, localization, and interactions with other molecules. It is highly desirable to have robust redox proteomics methods that can provide global, site-specific, and stoichiometric quantification of redox PTMs in order to elucidate the complex redox landscape and identify novel redox regulators in signaling and regulation. Mass spectrometry-based redox proteomics has emerged as the primary platform for enabling the broad characterization of thiol PTMs in cells and tissues. Herein we review recent advances in MS-based redox proteomics approaches for quantitative profiling of redox PTMs in cells and tissues at physiological or oxidative stress conditions and highlight some recent applications using these enabling techniques. Considering the relative maturity of available methods, a primary emphasis will be on two types of modifications: 1) total oxidation (i.e., all reversible thiol modifications), the level of which represents the overall redox state, and 2) S-glutathionylation, a major form of reversible thiol oxidation. We also discuss the significance of stoichiometric measurements of thiol PTMs as well as future perspectives towards a better understanding of cellular redox regulatory networks in cells and tissues.

59 BASIC BIOLOGICAL SCIENCES↗