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All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Infrared Spectra of Substituted Polycyclic Aromatic Hydrocarbons

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of 1-methylanthracene, 9-methylanthracene, 9-cyanoanthracene, 2-aminoanthracene, acridine, and their positive ions. The theoretical data are compared with matrix-isolation spectra for these species also reported in this work. The theoretical and experimental frequencies and relative intensities for the neutral species are in generally good agreement, whereas the positive ion spectra are only in qualitative agreement. Relative to anthracene, we find that substitution of amethyl or CN for a hydrogen does not significantly affect the spectrum other than to add the characteristic methyl C-H stretch and C-N stretch (near 2200/cm), respectively. However, addition of NH2 dramatically affects the spectrum of the neutral. Not only are the NH2 modes themselves strong, but this electron withdrawing group induces sufficient partial charge on the ring to give the neutral molecule characteristics of the anthracene cation spectrum. The sum of the absolute intensities is about four times larger for 2-aminoanthracene than for 9-cyanoanthracene. Substituting nitrogen in the ring at the nine position (acridine) does not greatly alter the spectrum compared with anthracene.

Bauschlicher, Charles W., Jr.↗
NASA NTRS2002

An Accurate Quartic Force Field, Fundamental Frequencies, and Binding Energy for the High Energy Density Material T(d)N4

The CCSD(T) method has been used to compute a highly accurate quartic force field and fundamental frequencies for all N-14 and N-15 isotopomers of the high energy density material T(sub d)N(sub 4). The computed fundamental frequencies show beyond doubt that the bands observed in a matrix isolation experiment by Radziszewski and coworkers are not due to different isotopomers of T(sub d)N(sub 4). The most sophisticated thermochemical calculations to date yield a N(sub 4) -> 2N(sub 2) heat of reaction of 182.22 +/- 0.5 kcal/mol at 0 K (180.64 +/- 0.5 at 298 K). It is hoped that the data reported herein will aid in the ultimate detection of T(sub d)N(sub 4).

Lee, Timothy J.↗
NASA NTRS2003

Studies of Atomic Free Radicals Stored in a Cryogenic Environment

Impurity-Helium Solids are porous gel-like solids consisting of impurity atoms and molecules surrounded by thin layers of solid helium. They provide an ideal medium for matrix isolation of free radicals to prevent recombination and store chemical energy. In this work electron spin resonance, nuclear magnetic resonance, X-ray diffraction, and ultrasound techniques have all been employed to study the properties of these substances. Detailed studies via electron spin resonance of exchange tunneling chemical reactions involving hydrogen and deuterium molecular and atomic impurities in these solids have been performed and compared with theory. Concentrations of hydrogen approaching the quantum solid criterion have been produced. Structured studies involving X ray diffraction, ultrasound, and electron spin resonance have shown that the impurities in impurity helium solids are predominantly contained in impurity clusters, with each cluster being surrounded by thin layers of solid helium.

Lee, David M.↗
NASA NTRS2003

The Lifetimes of Nitriles (-C*N) and Acids (-COOH) during Ultraviolet Photolysis and Their Survival in Space

Nitriles are one of the most common classes of molecules observed in the gas phase in space, with over a dozen having been positively identified in interstellar and circumstellar environments through the detection of their rotational transitions. Acids, in contrast, are much less common. In this paper we present laboratory data comparing the stability of two structurally related acid-nitrile pairs to ultraviolet (UV) photolytic destruction: acetic acid vs. acetonitrile (CH3-COOH vs. CH3-CN) and glycine vs. aminoacetonitrile (H2N-CH2-COOH vs. H2N-CH2-CN). We find that the nitriles are destroyed ten and five times more slowly (respectively) by UV photolysis than are the corresponding acids. This suggests that whatever their relative formation rates, acids may be less abundant than nitriles in interstellar environments in part because they are more rapidly destroyed by photolysis. The results of this infrared (IR) spectral matrix isolation study indicate that during the lifetime of a typical interstellar cloud, even in its darkest regions, a population of acids in the gas phase will likely be diminished by at least half. Since aminoacetonitrile is a precursor to the amino acid glycine, and far more stable, presolar aminoacetonitrile may be a contributor to the deuterium enriched glycine detected in meteorites. It would clearly be informative to search for aminoacetonitrile (the nitrile corresponding to glycine) in the regions where the amino acid glycine has been reported.

Bernstein, Max P.↗
NASA NTRS1998

Infrared spectra of substituted polycylic aromatic hydrocarbons

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of 1-methylanthracene, 9-methylanthracene, 9-cyanoanthracene, 2-aminoanthracene, acridine, and their positive ions. The theoretical data are compared with matrix-isolation spectra for these species also reported in this work. The theoretical and experimental frequencies and relative intensities for the neutral species are in generally good agreement, whereas the positive ion spectra are only in qualitative agreement. Relative to anthracene, we find that substitution of a methyl or CN for a hydrogen does not significantly affect the spectrum other than to add the characteristic methyl C-H and C triple bond N stretches near 2900 and 2200 cm-1, respectively. However, addition of NH2 dramatically affects the spectrum of the neutral. Not only are the NH2 modes themselves strong, but this electron-withdrawing group induces sufficient partial charge on the ring to give the neutral molecule spectra characteristics of the anthracene cation. The sum of the absolute intensities is about four times larger for 2-aminoanthracene than those for 9-cyanoanthracene. Substituting nitrogen in the ring at the nine position (acridine) does not greatly alter the spectrum compared with anthracene.

NASA Discipline Exobiology↗
NASA NTRS1991

Laboratory studies of the newly discovered infrared band at 4705.2 cm-1 (2.1253 micrometers) in the spectrum of Io: the tentative identification of CO2

We discuss over 120 laboratory experiments pertaining to the identification of the new absorption band discovered by Trafton et al. (1991) at 4705.2 cm-1 (2.1253 micrometers) in the spectrum of Io. It is shown that this band is not due to overtones or combinations of the fundamental bands associated with the molecules (or their chemical complexes) already identified on Io, namely, SO2, H2S, and H2O. Thus, this band is due to a new, previously unidentified, component of Io. Experiments also demonstrate that the band is not due to molecular H2 frozen in SO2 frosts. Since the frequency of this band is very close to the first overtone of the nu 3 asymmetric stretching mode of CO2, we have investigated the spectral behavior of CO2 under a variety of conditions appropriate for Io. The profile of the Io band is not consistent with the rotational envelope expected for single, freely rotating, gaseous CO2 under Io-like conditions. It was found that pure, solid CO2 and CO2 intimately mixed in a matrix of solid SO2 and H2S produce bands with similar widths (5-10 cm-1), but that these bands consistently fall at frequencies about 10-20 cm-1 (approximately 0.007 micrometer) lower than the Io band. CO2 in SO2 : H2S ices also produces several additional bands that are not in the Io spectra. The spectral fit improves, however, as the CO2 concentration in SO2 increases, suggesting that CO2-CO2 interactions might be involved. A series of Ar : CO2 and Kr : CO2 matrix isolation experiments, as well as laboratory work done elsewhere, show that CO2 clustering shifts the band position to higher frequencies and provides a better fit to the Io band. Various laboratory experiments have shown that gaseous CO2 molecules have a propensity to cluster between 80 and 100 K, temperatures similar to those found on the colder regions of Io. We thus tentatively identify the newly discovered Io band at 4705.2 cm-1 (2.1253 micrometers) with CO2 multimers or "clusters" on Io. Whether these clusters are buried within an SO2 frost, reside on the surface, or are in a residual, steady-state "atmospheric aerosol" population over local coldtraps is not entirely clear, although we presently favor the latter possibility. The size of these clusters is not well defined, but evidence suggests groups of more than four molecules are required. The absorption strength of the 2 nu 3 CO2 cluster overtone determined in the laboratory, in conjunction with the observed strength of the Io band, suggests that the disk-integrated abundance of CO2 is less than 1% that of the SO2. Studies of the sublimation behavior of CO2 indicate that it probably resides predominantly in the cooler areas (< 100 K) of Io. The relative constancy of the Io feature over a variety of orbital phases suggests that the polar regions may contain much of the material. Some consequences of the physical properties of CO2 under conditions pertinent to Io are discussed. The presence of CO2 clusters on Io could be verified by the detection of any one of several other infrared bands associated with the CO2 molecule, of which the strongest are the nu 3 12CO2 asymmetric stretch fundamental near 2350 cm-1 (4.25 micrometers) and the nu 2 bending mode fundamental near 660 cm-1 (15.1 micrometers). Weaker bands that may also be detectable include the nu 3 13CO2 asymmetric stretch fundamental near 2280 cm-1 (4.39 micrometers), the 2 nu 2 + nu 3 combination/overtone band near 3600 cm-1 (2.78 micrometers), and the nu 1 + nu 3 combination band near 3705 cm-1 (2.70 micrometers).

NASA Center ARC↗
NASA NTRS2019

PAH Clusters as Interstellar Very Small Grains

PAH clusters are one candidate species for the interstellar "very small grains" or "VSGs", i.e., dust grains small enough to be stochastically heated and contribute to the aromatic infrared emission bands (AIBs). This possibility motivated laboratory experiments on the infrared spectroscopy of PAH clusters using matrix isolation spectroscopy. The spectral shifts due to PAH clustering in argon matrices provide clues for the AIB contribution from PAH clusters in the interstellar medium. Here we review results from a number of small PAH species, extrapolation to the much larger PAHs believed to be present in the interstellar medium, and the implications for a PAH cluster contribution to the VSG population.

AIBs↗
NASA NTRSDate not supplied

In-Situ Alloying of GRCop-42 via Additive Manufacturing: Precipitate Analysis

GRCop-42, a Cu-4at% Cr-2at% Nb alloy, was designed as a high temperature, high strength, high heat flux material for rocket engine combustion chamber liners by NASA Glenn Research Center. In situ alloying of GRCop-42 (ISGRCop-42) using powder bed fusion (PBF) additive manufacturing (AM) takes elemental powders of Cu, Cr, and Nb to be introduced into the PBF environment and develop the GRCop alloy while simultaneously building an AM component. Elemental powders were milled together prior to printing in an effort to facilitate the alloying process. Success of the in situ alloying process may provide lower cost, faster lead times, alloying optimization, and more design freedom in the development of regeneratively-cooled rocket propulsion systems. Evaluation of the ISGRCop-42 was conducted using a phase extraction procedure to isolate the Cr2Nb precipitates from the pure Cu matrix. The isolated precipitates were then examined using x-ray powder diffraction (XRD), scanning electron microscopy (SEM), and energy dispersion spectroscopy (EDS). It was found that ISGRCop-42 successfully and repeatedly formed Cr2Nb at a yield as high as 89% of potential Cr2Nb. Further, it was identified that the preparation of the powder was the most influential factor in alloying success, and the second most influential factor was the laser power.

In Situ alloying↗
NASA NTRS1992

Studies of matrix vesicle-induced mineralization in a gelatin gel

Matrix vesicles isolated from fourth-passage cultures of chondrocytes were tested for their ability to induce hydroxyapatite formation in a gelatin gel in order to gain insight into the function of matrix vesicles in in situ mineralization. These matrix vesicles did not appear to be hydroxyapatite nucleators per se since the extent of mineral accumulation in the gel diffusion system was not altered by the presence of matrix vesicles alone, and in the vesicle containing gels, mineral crystals were formed whether associated with vesicles or not. In gels with these matrix vesicles and beta-glycerophosphate, despite the presence of alkaline phosphatase activity, there was no increase in mineral deposition. This suggested that in the gel system these culture-derived vesicles did not increase local phosphate concentrations. However, when known inhibitors of mineral crystal formation and growth (proteoglycan aggregates [4 mg/ml], or ATP [1 mM], or both proteoglycan and ATP) were included in the gel, more mineral was deposited in gels with the vesicles than in comparable gels without vesicles, indicating that enzymes within these vesicles were functioning to remove the inhibition. These data support the suggestion that one function of the extracellular matrix vesicles is to transport enzymes for matrix modification.

Non-NASA Center↗
NASA NTRS1993

Occurrence and possible significance of rare Ti oxides (Magneli phases) in carbonaceous chondrite matrices

Rare, ultrafine-grained Ti oxides (Ti3O5 and the Magneli phases, Ti5O9 and Ti8O15) have been identified by TEM in the CM2 carbonaceous chondrite, Bells, and a carbonaceous chondrite matrix clast from the Nilpena polymict ureilite. In both meteorites the Ti oxides occur in the matrix as isolated grains and clusters of two or more grains. They are euhedral in shape and have grain sizes of 0.05-0.3 micron. Magneli phases have been recently shown to be a common component in some interplanetary dust particles, but this is the first reported occurrence in a meteorite. The morphological properties and grain size of the Ti oxides are consistent with formation by vapor phase condensation either within the solar nebula or possibly in a presolar environment.

Brearley, Adrian J.↗
NASA NTRS1992

Casein kinase II protein kinase is bound to lamina-matrix and phosphorylates lamin-like protein in isolated pea nuclei

A casein kinase II (CK II)-like protein kinase was identified and partially isolated from a purified envelope-matrix fraction of pea (Pisum sativum L.) nuclei. When [gamma-32P]ATP was directly added to the envelope-matrix preparation, the three most heavily labeled protein bands had molecular masses near 71, 48, and 46 kDa. Protein kinases were removed from the preparation by sequential extraction with Triton X-100, EGTA, 0.3 M NaCl, and a pH 10.5 buffer, but an active kinase still remained bound to the remaining lamina-matrix fraction after these treatments. This kinase had properties resembling CK II kinases previously characterized from animal and plant sources: it preferred casein as an artificial substrate, could use GTP as efficiently as ATP as the phosphoryl donor, was stimulated by spermine, was calcium independent, and had a catalytic subunit of 36 kDa. Some animal and plant CK II kinases have regulatory subunits near 29 kDa, and a lamina-matrix-bound protein of this molecular mass was recognized on immunoblot by anti-Drosophila CK II polyclonal antibodies. Also found associated with the envelope-matrix fraction of pea nuclei were p34cdc2-like and Ca(2+)-dependent protein kinases, but their properties could not account for the protein kinase activity bound to the lamina. The 71-kDa substrate of the CK II-like kinase was lamin A-like, both in its molecular mass and in its cross-reactivity with anti-intermediate filament antibodies. Lamin phosphorylation is considered a crucial early step in the entry of cells into mitosis, so lamina-bound CK II kinases may be important control points for cellular proliferation.

NASA Discipline Plant Biology↗
NASA NTRS2009

Analytic Confusion Matrix Bounds for Fault Detection and Isolation Using a Sum-of-Squared- Residuals Approach

Given a system which can fail in 1 or n different ways, a fault detection and isolation (FDI) algorithm uses sensor data in order to determine which fault is the most likely to have occurred. The effectiveness of an FDI algorithm can be quantified by a confusion matrix, which i ndicates the probability that each fault is isolated given that each fault has occurred. Confusion matrices are often generated with simulation data, particularly for complex systems. In this paper we perform FDI using sums of squares of sensor residuals (SSRs). We assume that the sensor residuals are Gaussian, which gives the SSRs a chi-squared distribution. We then generate analytic lower and upper bounds on the confusion matrix elements. This allows for the generation of optimal sensor sets without numerical simulations. The confusion matrix bound s are verified with simulated aircraft engine data.

Simon, Dan↗
NASA NTRS1993

Embryonic lung morphogenesis in organ culture: experimental evidence for a proteoglycan function in the extracellular matrix

The lung rudiment, isolated from mid-gestation (11 day) mouse embryos, can undergo morphogenesis in organ culture. Observation of living rudiments, in culture, reveals both growth and ongoing bronchiolar branching activity. To detect proteoglycan (PG) biosynthesis, and deposition in the extracellular matrix, rudiments were metabolically labeled with radioactive sulfate, then fixed, embedded, sectioned and processed for autoradiography. The sulfated glycosaminoglycan (GAG) types, composing the carbohydrate component of the proteoglycans, were evaluated by selective GAG degradative approaches that showed chondroitin sulfate PG principally associated with the interstitial matrix, and heparan sulfate PG principally associated with the basement membrane. Experiments using the proteoglycan biosynthesis disrupter, beta-xyloside, suggest that when chondroitin sulfate PG deposition into the ECM is perturbed, branching morphogenesis is compromised.

NASA Discipline Number 93-10↗
NASA NTRS1984

Occurrence of oxidized components in Qingzhen enstatite chondrite

It is shown that the most unequilibrated enstatite chondrite, Qingzhen, contains a population of enstatite grains which appear to have formed under more oxidizing nebular conditions than the bulk of the meteorite, which is highly reduced. These grains are black in transmitted light because of the presence of micron-sized inclusions of Ni-poor, Cr-rich metal, and occur either isolated within the matrix or in chondrule interiors. The textural occurrence of these grains argues against their having been introduced during collision of Qingzhen with an oxidized meteorite. Most likely, they originated in the same general nebular neighborhood of the reduced bulk Qingzhen material and were subsequently transported into the reducing environment either before or during the process of chondrule formation. The discovery of this once-oxidized material in Qingzhen posed significant constraints on existing models of formation of reduced matter in the solar system.

Rambaldi, E. R.↗
NASA NTRS1988

Optoelectronic techniques for broadband switching

Optoelectronic switching employs a hybrid optical/electronic principle to perform the switching function and is applicable for either analog broadband or high-bit rate digital switching. The major advantages of optoelectronic switching include high isolation, low crosstalk, small physical size, light weight, and low power consumption. These advantages make optoelectronic switching an excellent candidate for on-board satellite switching. This paper describes a number of optoelectronic switching architectures. System components required for implementing these switching architectures are discussed. Performance of these architectures are evaluated by calculating their crosstalk, isolation, insertion loss, matrix size, drive power, throughput, and switching speed. Technologies needed for monolithic optoelectronic switching are also identified.

Su, S. F.↗
NASA NTRS1993

Effect of metamorphism on isolated olivine grains in CO3 chondrites

The presence of a metamorphic sequence in the CO3 chondrite group has been shown previously to result in changes in properties of chondrule silicates. However, the role of isolated olivine grains during metamorphism of these chondrites has not been addressed. Isolated olivine grains in two metamorphosed CO3 chondrites, Lance and Isna, have been investigated in this study in order to assess the compositional properties of isolated olivine grains that may be attributable to metamorphism. Compositional changes in isolated olivines with increasing petrologic subtype are very similar to changes in chondrule olivines in the same chondrites. Olivine compositions from all occurrences (chondrules, isolated grains, and matrix) converge with increasing petrologic subtype. The degree of equilibration of minor elements is qualitatively related to the diffusion rate of each element in olivine, suggesting that diffusion-controlled processes are the most important processes responsible for compositional changes within the metamorphic sequence. The data are consistent with metamorphism taking place in a closed system on the CO3 chondrite parent body. Fe-poor olivine grains in metamorphosed chondrites are characterized by an Fe-rich rim, which is the result of diffusion of Fe into the grains from Fe-rich matrix. In some instances, 'complex', Fe-rich rims have been identified, which appear to have originated as igneous overgrowths and subsequently to have been overprinted by diffusion processes during metamorphism. Processes experienced by CO3 chondrites are more similar to those experienced by the ordinary chondrites than to those encountered by other carbonaceous chondrites, such as the CV3 group.

Jones, Rhian H.↗
NASA NTRS1974

Vibrational spectrum of CO2/-/ in an argon matrix

Ar:CO:N2O samples of mole ratio 250:1:1 and 500:1:1 were codeposited at 14 K with an atomic beam of sodium or potassium. The infrared spectrum of the resulting deposit was basically identical to that for CO and N2O isolated in an argon matrix in the absence of alkali metal atoms. Spectral absorption features were studied of Ar:CO2 samples of mole ratio ranging from 250 to 500 codeposited with an atomic beam of potassium. Ar:CO2 samples with a mole ratio in the range from 250 to 1000, which had been codeposited with an atomic beam of cesium, were also investigated.

Jacox, M. E.↗
NASA NTRS2012

Deducing Wild 2 Components with a Statistical Dataset of Olivine in Chondrite Matrix

Introduction: A preliminary exam of the Wild 2 olivine yielded a major element distribution that is strikingly similar to those for aqueously altered carbonaceous chondrites (CI, CM, and CR) [1], in which FeO-rich olivine is preferentially altered. With evidence lacking for large-scale alteration in Wild 2, the mechanism for this apparent selectivity is poorly understood. We use a statistical approach to explain this distribution in terms of relative contributions from different chondrite forming regions. Samples and Analyses: We have made a particular effort to obtain the best possible analyses of both major and minor elements in Wild 2 olivine and the 5-30 micrometer population in chondrite matrix. Previous studies of chondrite matrix either include larger isolated grains (not found in the Wild 2 collection) or lack minor element abundances. To overcome this gap in the existing data, we have now compiled greater than 10(exp 3) EPMA analyses of matrix olivine in CI, CM, CR, CH, Kakangari, C2-ungrouped, and the least equilibrated CO, CV, LL, and EH chondrites. Also, we are acquiring TEM/EDXS analyses of the Wild 2 olivine with 500s count times, to reduce relative errors of minor elements with respect to those otherwise available. Results: Using our Wild 2 analyses and those from [2], the revised major element distribution is more similar to anhydrous IDPs than previous results, which were based on more limited statistics (see figure below). However, a large frequency peak at Fa(sub 0-1) still persists. All but one of these grains has no detectable Cr, which is dissimilar to the Fa(sub 0-1) found in the CI and CM matrices. In fact, Fa(sub 0-1) with strongly depleted Cr content is a composition that appears to be unique to Kakangari and enstatite (highly reduced) chondrites. We also note the paucity of Fa(sub greater than 58), which would typically indicate crystallization in a more oxidizing environment [3]. We conclude that, relative to the bulk of anhydrous IDPs, Wild 2 may have received a larger contribution from the Kakangari and/or enstatite chondrite forming regions. Alternatively, Wild 2 may have undergone accretion in an anomalously reducing region, marked by nebular condensation of this atypical forsterite. In [4], a similar conclusion was reached with an Fe-XANES study. We will also use similar lines of reasoning, and our previous conclusions in [5], to constrain the relative contributions of silicates that appear to have been radially transported from different ordinary and carbonaceous chondrite forming regions to the Kuiper Belt. In addition, the widespread depletion of Cr in these FeO-rich (Fa(sub greater than 20)) fragments is consistent with mild thermal metamorphism in Wild 2.

Frank, D. R.↗