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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

An algorithm for converting a virtual-bond chain into a complete polypeptide backbone chain

A systematic analysis is presented of the algorithm for converting a virtual-bond chain, defined by the coordinates of the alpha-carbons of a given protein, into a complete polypeptide backbone. An alternative algorithm, based upon the same set of geometric parameters used in the Purisima-Scheraga algorithm but with a different "linkage map" of the algorithmic procedures, is proposed. The global virtual-bond chain geometric constraints are more easily separable from the loal peptide geometric and energetic constraints derived from, for example, the Ramachandran criterion, within the framework of this approach.

NASA Discipline Exobiology↗
NASA NTRS1991

Ab initio study of the electrostatic multipole nature of torsional potentials in CH3SSCH3, CH3SSH, and HOOH

The origin of torsional potentials in H3CSSCH3, H3CSSH, and HOOH and the anisotropy of the local charge distribution has been analyzed in terms of atomic multipoles calculated from the ab initio LCAO-MO-SCF wave function in the 6-31G* basis set. The results indicate that for longer -S-S-bonds the major contribution to these torsional barriers are electrostatic interactions of the atomic multipoles located on two atoms forming the rotated bond. This finding demonstrates the important role of electrostatic 1-2 interatomic interactions, usually neglected in conformational studies. It also opens the possibility to derive directly from accurate ab initio wave functions a simple nonempirical torsional potential involving atomic multipoles of two bonded atoms defining the torsional angle. For shorter -O-O- bonds, use of more precise models and inclusion of 1-3 interactions seems to be necessary.

NASA Program Exobiology↗
NASA NTRS1991

Box models for the evolution of atmospheric oxygen: an update

A simple 3-box model of the atmosphere/ocean system is used to describe the various stages in the evolution of atmospheric oxygen. In Stage I, which probably lasted until redbeds began to form about 2.0 Ga ago, the Earth's surface environment was generally devoid of free O2, except possibly in localized regions of high productivity in the surface ocean. In Stage II, which may have lasted for less than 150 Ma, the atmosphere and surface ocean were oxidizing, while the deep ocean remained anoxic. In Stage III, which commenced with the disappearance of banded iron formations around 1.85 Ga ago and has lasted until the present, all three surface reservoirs contained appreciable amounts of free O2. Recent and not-so-recent controversies regarding the abundance of oxygen in the Archean atmosphere are identified and discussed. The rate of O2 increase during the Middle and Late Proterozoic is identified as another outstanding question.

NASA Program Exobiology↗
NASA NTRS1992

Cumulative atomic multipole moments complement any atomic charge model to obtain more accurate electrostatic properties

The quality of several atomic charge models based on different definitions has been analyzed using cumulative atomic multipole moments (CAMM). This formalism can generate higher atomic moments starting from any atomic charges, while preserving the corresponding molecular moments. The atomic charge contribution to the higher molecular moments, as well as to the electrostatic potentials, has been examined for CO and HCN molecules at several different levels of theory. The results clearly show that the electrostatic potential obtained from CAMM expansion is convergent up to R-5 term for all atomic charge models used. This illustrates that higher atomic moments can be used to supplement any atomic charge model to obtain more accurate description of electrostatic properties.

NASA Discipline Number 52-20↗
NASA NTRS1993

Carbon and nitrogen isotopic compositions of alkyl porphyrins from the Triassic Serpiano oil shale

The carbon and nitrogen isotopic compositions of seven of the most abundant alkylporphyrins from the Serpiano oil shale (marine, Triassic) were determined. For the C31 and C32 butanoporphyrins, values of delta 13CPDB and delta 15NAIR averaged -24.0% and -3.1%. In contrast, the C31 and C32 methylpropanoporphyrins, DPEP, and a C30 13-nor etioporphyrin had delta 13C and delta 15N values averaging -27.5 and -3.3%, respectively. Carbon and nitrogen isotopic values for kerogen averaged -30.8 and -0.9, whereas those for total extract averaged -31.6, and -4.0%. The butanoporphyrins apparently derive from a biological source different from that giving rise to the other porphyrins, their 13C enrichment not being related to carbon isotopic fractionation accompanying diagenetic reactions. The delta 15N values for all the porphyrins indicate that the depletion of 15N observed in the kerogen is of primary origin. Consistent with the very high abundance of hopanoids and methyl hopanoids in the aliphatic hydrocarbon fraction, it is suggested that cyanobacterial fixation of N2 may have been the main cause of 15N depletion.

NASA Discipline Exobiology↗
NASA NTRS1988

Cyclization of nucleotide analogues as an obstacle to polymerization

Cyclization of activated nucleotide analogues by intramolecular phosphodiester-bond formation is likely to compete very effectively with template-directed condensation except in the cases of ribo- and arabinonucleotides. This could have excluded derivatives of most sugars from growing polyribonucleotide chains and thus reduced chain-termination in prebiotic polynucleotide synthesis.

NASA Discipline Exobiology↗
NASA NTRS2005

Ice Forming Regions during Evolution of the Solar Nebula

The condensation/sublimation front using a two dimensional model of the evolving solar system is investigated based on combined viscous and radiative heating. The snow line is shown to be a two-branched curve reflecting the competing effects of solar heating in the photosphere and internal heating at the center plane. The evolution of the icy region is described from a limited region early in the disk evolution to final positions near 1 AU. The snow line evolution predicted using two surface density models, a Hayashi minimum mass power law and an analytical solution of the nebula evolution equation. Possible effects of this dynamic motion on disk chemistry and organic molecule formation is also described.

Davis, Sanford S.↗
NASA NTRS2006

Following the Water: the Evolution of Ice-forming Regions in the Early Solar Nebula

The abundances of water-vapor and water-ice during the first ten million years of the protoplanetary solar nebula are simulated using a new condensation/sublimation model. This study builds on a "snow line" model reported in ApJ 627 L153 (2005); it uses a simple phenomenological model where water vapor molecules evolve from solar atomic abundance and eventually condenses to ice at colder points in the nebula once the water-vapor partial pressure exceeds a value determined by the phase diagram for water. The synthesis of water vapor from elementary species is modeled with a chemical network consisting of about 400 species and 4000 reactions. The evolution of the icy zone (and its relative abundance of solid ice) is traced from a limited region in the early hotter disk to its final state at the time when the gas is expelled and a planetary system begins to form. Possible effects of this dynamic motion on disk chemistry and organic molecule formation are also described.

Davis, Sanford S.↗
NASA NTRS2013

Infrared Spectra and Optical Constants of Astronomical Ices: I. Amorphous and Crystalline Acetylene

Here we report recent measurements on acetylene (C2H2) ices at temperatures applicable to the outer Solar System and the interstellar medium. New near- and mid-infrared data, including optical constants (n, k), absorption coefficients (alpha), and absolute band strengths (A), are presented for both amorphous and crystalline phases of C2H2 that exist below 70 K. Comparisons are made to earlier work. Electronic versions of the data are made available, as is a computer routine to use our reported n and k values to simulate the observed IR spectra. Suggestions are given for the use of the data and a comparison to a spectrum of Makemake is made.

IR spectroscopy↗
NASA NTRS2014

Infrared Spectra and Optical Constants of Astronomical Ices: II. Ethane and Ethylene

Infrared spectroscopic observations have established the presence of hydrocarbon ices on Pluto and other TNOs, but the abundances of such molecules cannot be deduced without accurate optical constants (n, k) and reference spectra. In this paper we present our recent measurements of near- and mid-infrared optical constants for ethane (C2H6) and ethylene (C2H4) in multiple ice phases and at multiple temperatures. As in our recent work on acetylene (C2H2), we also report new measurements of the index of refraction of each ice at 670 nm. Comparisons are made to earlier work where possible, and electronic versions of our new results are made available.

Ices↗
NASA NTRS2016

Stratospheric Aerosol--Observations, Processes, and Impact on Climate

Interest in stratospheric aerosol and its role in climate have increased over the last decade due to the observed increase in stratospheric aerosol since 2000 and the potential for changes in the sulfur cycle induced by climate change. This review provides an overview about the advances in stratospheric aerosol research since the last comprehensive assessment of stratospheric aerosol was published in 2006. A crucial development since 2006 is the substantial improvement in the agreement between in situ and space-based inferences of stratospheric aerosol properties during volcanically quiescent periods. Furthermore, new measurement systems and techniques, both in situ and space based, have been developed for measuring physical aerosol properties with greater accuracy and for characterizing aerosol composition. However, these changes induce challenges to constructing a long-term stratospheric aerosol climatology. Currently, changes in stratospheric aerosol levels less than 20% cannot be confidently quantified. The volcanic signals tend to mask any nonvolcanically driven change, making them difficult to understand. While the role of carbonyl sulfide as a substantial and relatively constant source of stratospheric sulfur has been confirmed by new observations and model simulations, large uncertainties remain with respect to the contribution from anthropogenic sulfur dioxide emissions. New evidence has been provided that stratospheric aerosol can also contain small amounts of nonsulfatematter such as black carbon and organics. Chemistry-climate models have substantially increased in quantity and sophistication. In many models the implementation of stratospheric aerosol processes is coupled to radiation and/or stratospheric chemistry modules to account for relevant feedback processes.

Kresmer, Stefanie↗
NASA NTRS2012

The Formation Heritage of Jupiter Family Comet 10P/Tempel 2 as Revealed by Infrared Spectroscopy

We present spectral and spatial information for major volatile species in Comet 10P/Tempel 2, based on high-dispersion infrared spectra acquired on UT 2010 July 26 (heliocentric distance R h = 1.44 AU) and September 18 (R h = 1.62 AU), following the comet’s perihelion passage on UT 2010 July 04. The total production rate for water on July 26 was (1.90 ± 0.12) × 10 28 molecules s −1 , and abundances of six trace gases (relative to water) were: CH 3 OH (1.58% ± 0.23%), C 2 H 6 (0.39% ± 0.04%), NH 3 (0.83% ± 0.20%), and HCN (0.13% ± 0.02%). A detailed analysis of intensities for water emission lines provided a rotational temperature of 35 ± 3 K. The mean OPR is consistent with nuclear spin populations in statistical equilibrium (OPR = 3.01 ± 0.18), and the (1σ) lower bound corresponds to a spin temperature >38 K. Our measurements were contemporaneous with a jet-like feature observed at optical wavelengths. The spatial profiles of four primary volatiles display strong enhancements in the jet direction, which favors release from a localized vent on the nucleus. The measured IR continuum is much more sharply peaked and is consistent with a dominant contribution from the nucleus itself. The peak intensities for H 2 O, CH 3 OH, and C 2 H 6 are offset by ∼200 km in the jet direction, suggesting the possible existence of a distributed source, such as the release of icy grains that subsequently sublimed in the coma. On UT September 18, no obvious emission lines were present in our spectra, nevertheless we obtained a 3σ upper limit Q(H 2 O) < 2.86 × 10 27 molecules s −1 .

Organic Chemistry↗
NASA NTRSDate not supplied

Calibration and Validation of the SHERLOC Instrument Operating in Jezero Crater, Mars

The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemistry (SHERLOC) is an instrument onboard the Mars 2020 Perseverance rover. It consists of a spectrometer that measures deep ultraviolet (DUV) resonance Raman and native fluorescence photons generated through surface interactions with a 248.6 nm pulsed laser. Two microscopic imagers, the Autofocus Context Imager (ACI) and the Wide-Angle Topographic Sensor for Operations and eNgineering (WATSON), provide high-resolution context images of SHERLOC targets. The ACI is co-boresighted with the spectrometer. To ensure proper calibration, the SHERLOC calibration target (SCT) is mounted on the front of the rover and consists of ten different materials. The SCT was designed, fabricated, assembled, and tested by Jacobs Technology, Inc., and NASA Johnson Space Center. The dimensions of the calibration target housing are 150 x 89 x 33 mm and it weighs ~437 g. The ten targets are arranged in two rows; the first six are hard targets (AlGaN for Raman and fluorescence, diffuse transmission target, a slice of the SaU008 Mars meteorite, an intensity maze, and polycarbonate over geocache coin) and the remaining four are soft-goods targets (Vectran, Ortho-Fabric, Teflon, and nGimat-coated Teflon). The hard targets calibrate the spectrometer’s Raman and fluorescence spectral accuracy, ambient light reflection, and Raman response curve, while the soft-goods targets are spacesuit materials that function as human exploration targets, some of which are also used for spectral calibration. SHERLOC also has an internal calibration target consisting of AlGaN on sapphire (275 nm) located inside the ACI opaque dust cover to ensure proper instrument functioning between calibration target analyses. Initial SHERLOC, ACI, and WATSON calibration and validation on Mars was performed using the internal calibration target on sols 59, 83, 98, and 141; WATSON imaging of the SCT on sols 26 and 62, and SHERLOC spectroscopy and ACI imaging of the SCT on sol 59. These early data provide initial insights into instrument performance and the stability and degradation of the calibration target materials relative to the Martian surface and dust environment. Early observations also have implications for future astronaut spacesuit materials.

Trevor G Graff↗
NASA NTRSDate not supplied

INCORPORATION OF NITROGEN INTO ORGANICS PRODUCED BY FISCHER-TROPSCH TYPE CHEMISTRY

Laboratory simulations have demonstrated that hydrothermal systems have the potential to produce a range of organic compounds through Fischer-Tropsch type (FTT) chemistry. The distribution of products depends on several factors, including the abundance and composition of feedstock molecules, reaction temperature, and the physical and chemical characteristics of catalytic materials included in the reactions. The majority of studies per-formed to date have focused solely on inclusion of CO2 or CO and H2 as the carbon, oxygen and hydrogen sources, which limits the possible products to hydrocarbons, alcohols and carboxylic acids. A few studies have included nitrogen in the form of ammonia, which led to the production of amino acids and nitrogenous bases. Although these demonstrations provide compelling evidence that FTT reactions can produce compounds of interest for the origins of life, such reactions have been conducted under a very limited range of conditions and the synthetic reaction mechanisms have generally not been well-characterized. We have begun a series of laboratory experiments that will incorporate a range of precursor molecules in varying compositions to determine how these variables affect the relative amounts and speciation of life-essential elements in organic molecules produced under FTT conditions. In the present work, we focus on systems containing C, H, O and N. Reaction mixtures contained CO (~60-80 mM), 150 mM ammonium chloride, and water with a native iron catalyst, which also served as a source of H2 through the reduction of water. Three initial experiments were conducted at 110, 154 and 185 °C and heated for several days. Following the reaction, samples were analyzed by gas chromatography-mass spectrometry, direct analysis in real time mass spectrometry and liquid chromatography-mass spectrometry.

A. S. Burton↗
NASA NTRS2020

Incorporation of Nitrogen into Organics Produced by Fischer-Tropsch Type Chemistry

Laboratory simulations have demonstrated that hydrothermal systems have the potential to produce a range of organic compounds through Fischer-Tropsch type (FTT) chemistry. The distribution of products depends on several factors, including the abundance and composition of feed-stock molecules, reaction temperature, and the physical and chemical characteristics of catalytic materials included in the reactions. The majority of studies per-formed to date have focused solely on inclusion of CO2 or CO and H2 as the carbon, oxygen and hydrogen sources, which limits the possible products to hydro-carbons, alcohols and carboxylic acids. A few studies have included nitrogen in the form of ammonia, which led to the production of amino acids and nitrogenous bases; and a separate suite of studies included sulfur as sulfide minerals or H2S, which yielded products such as thiols and amino acids. Although these demonstrations provide compelling evidence that FTT reactions can produce compounds of interest for the origins of life, such reactions have been conducted under a very limited range of conditions and the synthetic reaction mechanisms have generally not been well-characterized. As a consequence, it is difficult to extrapolate these results to geologic systems or to evaluate how variations in reactant compositions would affect the distribution of products over time. We have begun a series of laboratory experiments that will incorporate a range of precursor molecules in varying compositions to determine how these variables affect the relative amounts and speciation of life-essential elements in organic molecules produced under FTT conditions. In the present work, we focus on systems containing C, H, O and N.

Burton, A. S.↗
NASA NTRS2003

Oxygenated Organic Chemicals in the Pacific Troposphere: Distribution, Sources and Chemistry

Airborne measurements of a large number of oxygenated organic chemicals (Oxorgs) were carried out in the Pacific troposphere (0.1-12 km) in the Spring of 2001 (Feb. 24-April 10). Specifically these measuremen ts included acetone, methylethyl ketone (MEK), methanol, ethanol, ace taldehyde, propionaldehyde, PANS, and organic nitrates. Complementary measurements of formaldehyde, organic peroxides, and tracers were al so available. Ox-orgs were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Their mixing ratios were typically highest in the lower troposphere and declined toward s the upper troposphere and the lowermost stratosphere. Their total a bundance (Ox-orgs) significantly exceeded that of NMHC (C2-C8 NMHC). A comparison of these data with observations collected some seven yea rs earlier (Feb.-March, 1994), did not reveal any significant changes . Throughout the troposphere mixing ratios of Ox-orgs were strongly c orrelated with each other as well as with tracers of fossil and bioma sshiof'uel combustion. Analysis of the relative enhancement of selected Oxorgs with respect to CH3Cl and CO in twelve sampled plumes, origi nating from fires, is used to assess their primary and secondary sour ces from biomass combustion. The composition of these plumes also ind icates a large shift of reactive nitrogen into the PAN reservoir ther eby limiting ozone formation. The Harvard 3-D photochemical model, th at uses state of the art chemistry and source information, is used to compare simulated and observed mixing ratios of selected species. A 1 -D model is used to explore the chemistry of aldehydes. These results will be presented.

Singh, Hanwant B.↗
NASA NTRS1995

Evidence for organic synthesis in high temperature aqueous media - facts and prognosis

Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range - warm to greater than 400 C) is responsible for these molecular alterations, expulsion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. The reactivity of organic compounds in hot water (200-350 C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to greater than 400 C.

Simoneit, Bernd R. T.↗
NASA NTRS1992

Hydrothermal organic synthesis experiments

The serious scientific debate about spontaneous generation which raged for centuries reached a climax in the nineteenth century with the work of Spallanzani, Schwann, Tyndall, and Pasteur. These investigators demonstrated that spontaneous generation from dead organic matter does not occur. Although no aspects of these experiments addressed the issue of whether organic compounds could be synthesized abiotically, the impact of the experiments was great enough to cause many investigators to assume that life and its organic compounds were somehow fundamentally different than inorganic compounds. Meanwhile, other nineteenth-century investigators were showing that organic compounds could indeed be synthesized from inorganic compounds. In 1828 Friedrich Wohler synthesized urea in an attempt to form ammonium cyanate by heating a solution containing ammonia and cyanic acid. This experiment is generally recognized to be the first to bridge the artificial gap between organic and inorganic chemistry, but it also showed the usefulness of heat in organic synthesis. Not only does an increase in temperature enhance the rate of urea synthesis, but Walker and Hambly showed that equilibrium between urea and ammonium cyanate was attainable and reversible at 100 C. Wohler's synthesis of urea, and subsequent syntheses of organic compounds from inorganic compounds over the next several decades dealt serious blows to the 'vital force' concept which held that: (1) organic compounds owe their formation to the action of a special force in living organisms; and (2) forces which determine the behavior of inorganic compounds play no part in living systems. Nevertheless, such progress was overshadowed by Pasteur's refutation of spontaneous generation which nearly extinguished experimental investigations into the origins of life for several decades. Vitalism was dealt a deadly blow in the 1950's with Miller's famous spark-discharge experiments which were undertaken in the framework of the Oparin and Haldane hypotheses concerning the origin of life. These hypotheses were constructed on some basic assumptions which included a reduced atmosphere, and a low surface temperature for the early Earth. These ideas meshed well with the prevailing hypothesis of the 1940's and 50's that the Earth had formed through heterogeneous accretion of dust from a condensing solar nebula. Miller's experiments were extremely successful, and were followed by numerous other experiments by various investigators who employed a wide variety of energy sources for abiotic synthesis including spark discharges, ultra-violet radiation, heat, shock waves, plasmas, gamma rays, and other forms of energy. The conclusion reached from this body of work is that energy inputs can drive organic synthesis from a variety of inorganic starting materials.

Shock, Everett L.↗