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At least 829 records · Page 46
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NASA NTRS1987

The hydrogen coverage of interstellar PAHs

The rate at which the CH bond in interstellar Polycyclic Aromatic Hydrocarbons (PAHs) rupture due to the absorption of a UV photon has been calculated. The results show that small PAHs (less than or equal to 25 carbon atoms) are expected to be partially dehydrogenated in regions with intense UV fields, while large PAHs (greater than or equal to 25 atoms) are expected to be completely hydrogenated in those regions. Because estimate of the carbon content of interstellar PAHs lie in the range of 20 to 25 carbon atoms, dehydrogenation is probably not very important. Because of the absence of other emission features besides the 11.3 micrometer feature in ground-based 8 to 13 micrometer spectra, it has been suggested that interstellar PAHs are partially dehydrogenated. However, IRAS 8 to 22 micrometer spectra of most sources that show strong 7.7 and 11.2 micrometer emission features also show a plateau of emission extending from about 11.3 to 14 micrometer. Like the 11.3 micrometer feature, this new feature is attributed to the CH out of plane bending mode in PAHs. This new feature shows that interstellar PAHs are not as dehydrogenated as estimated from ground-based 8 to 13 micrometer spectra. It also constrains the molecular structure of interstellar PAHs. In particular, it seems that very condensed PAHs, such as coronene and circumcoronene, dominate the interstellar PAH mixture as expected from stability arguments.

Tielens, A. G. G. M.↗
NASA NTRS1986

Isoelectric focusing of dansylated amino acids in immobilized pH gradients

The 21 free amino acids commonly encountered in proteins have been transformed into 'carrier ampholyte' species by reacting their primary amino groups with dansyl chloride. These derivatives can thus be focused in an immobilized pH gradient covering the pH interval 3.1 to 4.1, except for arginine, which still retains a pI of 8.8. Due to their inherent fluorescence, the dansyl derivatives are revealed in UV light, with a sensitivity of the order of 2-4 ng/sq mm. All nearest neighbors are separated except for the following couples: Asn-Gln, Gly-Thr, Val-Ile and Cys-Cys2, with a resolving power, in a Delta(pI) scale, of the order of 0.0018 pH units. Except for a few cases (notably the aromatic amino acids), the order of pI values is well correlated with the pK values of carboxyl groups, suggesting that the latter are not altered by dansylation. From the set of pK(COOH)-pI values of the different amino acids, the pK of the tertiary amino group in the dansyl label has been calculated to be 5.11 + or - 0.06. Knowing the pK of the amino-dansyl and the pI of the excess, free dansyl label (pI = 3.34), a pK of 1.57 is derived for its sulfonic acid group.

Bianchi-Bosisio, Adriana↗
NASA NTRS1986

Composition, structure and chemistry of interstellar dust

The observational constraints on the composition of the interstellar dust are analyzed. The dust in the diffuse interstellar medium consists of a mixture of stardust (amorphous silicates, amorphous carbon, polycyclic aromatic hydrocarbons, and graphite) and interstellar medium dust (organic refractory material). Stardust seems to dominate in the local diffuse interstellar medium. Inside molecular clouds, however, icy grain mantles are also important. The structural differences between crystalline and amorphous materials, which lead to differences in the optical properties, are discussed. The astrophysical consequences are briefly examined. The physical principles of grain surface chemistry are discussed and applied to the formation of molecular hydrogen and icy grain mantles inside dense molecular clouds. Transformation of these icy grain mantles into the organic refractory dust component observed in the diffuse interstellar medium requires ultraviolet sources inside molecular clouds as well as radical diffusion promoted by transient heating of the mantle. The latter process also returns a considerable fraction of the molecules in the grain mantle to the gas phase.

Tielens, Alexander G. G. M.↗
NASA NTRS1988

Solar generation and storage of O2 (a 1 delta g)

An investigation was performed of the technical steps required to design a solar powered oxygen-iodine laser. Singlet delta oxygen is formed upon transfer of energy from selected photoexcited dye molecules to ground state molecular oxygen and then is concentrated and stored as an endoperoxide by reaction with an aromatic hydrocarbon. The endoperoxide, when heated, releases singlet oxygen in high yield thus providing a regenerable source of laser fuel. Energy transfer from dye molecules to molecular oxygen was investigated. When dye molecules were adsorbed to polymer substrates it was observed that the dye became embedded in the polymer matrix. Porphin dyes were incorporated into films of 1,4-dimethyl-2-poly(vinylnaphthalene), 2PVN. An endoperoxide was formed when porphin-doped 2PVN was exposed to visible radiation. This demonstrates the possibility of generating singlet oxygen using solar energy and concentrating and storing it in one simple step. Transport of energy by exciton migration in polycrystalline dye films was also investigated.

Twarowski, Allen J.↗
NASA NTRS1987

Composition, structure, and chemistry of interstellar dust

Different dust components present in the interstellar medium (IM) such as amorphous carbon, polycyclic aromatic hydrocarbons, and those IM components which are organic refractory grains and icy grain mantles are discussed as well as their relative importance. The physical properties of grain surface chemistry are discussed with attention given to the surface structure of materials, the adsorption energy and residence time of species on a grain surface, and the sticking probability. Consideration is also given to the contribution of grains to the gas-phase composition of molecular clouds.

Tielens, A. G. G. M.↗
NASA NTRS1987

Infrared absorption and emission characteristics of interstellar PAHs

The mid-infrared interstellar emission spectrum with features at 3.28, 6.2, 7.7, 8.7 and 11.3 microns is discussed in terms of the Polycyclic Aromatic Hydrocarbon (PAH) hypothesis, which is based on the suggestive, but inconclusive comparison between the interstellar emission spectrum with the infrared absorption and Raman spectra of a few PAHs. The fundamental vibrations of PAHs and PAH-like species which determine the IR and Raman properties are discussed. Interstellar IR band emission is due to relaxation from highly vibrationally excited PAHs excited by ultraviolet photons. The excitation/emission process is described and the IR fluorescence from one PAH, chrysene, is traced. Generally, there is sufficient energy to populate several vibrational levels in each mode. Molecular vibrational potentials are anharmonic and emission from these higher levels will fall at lower frequencies and produce weak features to the red of the stronger fundamentals. This process is also described and can account for some spectroscopic details of the interstellar emission spectra previously unexplained. Analysis of the interstellar spectrum shows that PAHs contain between 20 and 30 carbon atoms and are responsible for the emission.

Allamandola, L. J.↗
NASA NTRS1987

Infrared emission from interstellar PAHs

The mid-IR absorption and Raman spectra of polycyclic aromatic hydrocarbons (PAHs) and the mechanisms determining them are reviewed, and the implications for observations of similar emission spectra in interstellar clouds are considered. Topics addressed include the relationship between PAHs and amorphous C, the vibrational spectroscopy of PAHs, the molecular emission process, molecular anharmonicity, and the vibrational quasi-continuum. Extensive graphs, diagrams, and sample spectra are provided, and the interstellar emission bands are attributed to PAHs with 20-30 C atoms on the basis of the observed 3.3/3.4-micron intensity ratios.

Allamandola, L. J.↗
NASA NTRS1987

Evolution of interstellar dust

The composition, origins, and evolution of interstellar dust (ISD) are examined, reviewing the results of recent observational and theoretical investigations. Topics discussed include amorphous and polycrystalline structures; the relationship between amorphous C, graphite, and polycyclic aromatic hydrocarbons; observational techniques for determining ISD structure and composition; ISD formation in outflows from late-type giants, planetary nebulae, and novae; destruction of ISD by shocks; the formation of ISD in the ISM; and the relationship between ISD and interplanetary dust. IR spectroscopy of molecular ices and icy grain mantles is considered in detail, and it is shown that typical grain mantles consist of a 1/0.6/0.05/0.05 mixture of H2O, CH3OH, CO, and NH3.

Tielens, A. G. G. M.↗
NASA NTRS1988

High spectral resolution observations of HD 44179 at 3.2-3.7 microns

New high-resolution spectra of HD 44179 (the 'Red rectangle') in the 3.2-3.7 micron range are presented. Contrary to previous observations, no evidence is found for the 3.4 micron feature which is supposed to arise from aromatic hydrocarbons. The strong 3.29 micron feature is found to be different from that seen in NGC 7027 and IRAS 21282+5050.

Tokunaga, A. T.↗
NASA NTRS1988

Large molecules in diffuse interstellar clouds

The effects of the presence of a substantial component of large molecules on the chemistry of diffuse molecular clouds are explored, and detailed models of the zeta Persei and zeta Ophiuchi clouds are constructed. The major consequence is a reduction in the abundances of singly charged atomic species. The long-standing discrepancy between cloud densities inferred from rotational and fine-structure level populations and from the ionization balance can be resolved by postulating a fractional abundance of large molecules of 1 x 10 to the -7th for zeta Persei and 6 x 10 to the -7th for zeta Ophiuchi. If the large molecules are polycyclic aromatic hydrocarbons (PAH) containing about 50 carbon atoms, they contain 1 percent of the carbon in zeta Persei and 7 percent in zeta Ophiuchi. Other consequences of the possible presence of PAH molecules are discussed.

Lepp, S.↗
NASA NTRS1988

The size and composition of interstellar grains

Aspects of interstellar grains and their observations are discussed. The forms of solid carbon of which the grains can be composed are examined, and the nature of the 2175 A bump is discussed, taking into consideration two stars which show well-determined short-wavelength bump positions. The difficulties of assigning graphite as the only carrier of the bump are reviewed, and the properties of the 'far-ultraviolet rise' of the extinction for 1/lambda greater than 6/micron are considered. The properties of infrared emission bands and reasons for identifying the bands with aromatic hydrocarbons of some sort are examined. The properties of red and infrared emission are discussed, and possible connections with hydrogenated amorphous carbon are addressed.

Mathis, John S.↗
NASA NTRS1988

Adhesive properties of LARC-CPI, a new semi-crystalline polyimide

As part of an effort on high temperature structural resins for aerospace applications, a new family of polyimides containing carbon and ether connecting groups between aromatic rings were prepared. Several of these polyimides were semicrystalline. One polyimide, designated LARC-CPI, with a glass transition temperature of 222 C and a crystalline melt temperature of 350 C, was evaluated in the form of an adhesive, film, and molding. Unoriented films exhibited excellent resistance to solvents and strong bases and high tensile properties. Compact tension specimens gave very high fracture toughness values. Titanium tensile shear specimens provided exceptional strength under a variety of test conditions. The chemistry and the physical and mechanical properties of LARC-CPI are discussed.

Hergenrother, P. M.↗
NASA NTRS1989

Low-Dielectric Polyimides

New process developed to produce aromatic condensation polyimide films and coatings having dielectric constants in range of 2.4 to 3.2. Materials better electrical insulators than state-of-the-art commercial polyimides. Several low-dielectric-constant polyimides have excellent resistance to moisture. Useful as film and coating materials for both industrial and aerospace applications where high electrical insulation, resistance to moisture, mechanical strength, and thermal stability required. Applicable to production of high-temperature and moisture-resistance adhesives, films, photoresists, and coatings. Electronic applications include printed-circuit boards, both of composite and flexible-film types and potential use in automotive, aerospace, and electronic industries.

St. Clair, Anne K.↗
NASA NTRS1988

Cometary dust composition

The earth based measurements and in situ sampling of Comet Halley have provided new data about the chemical composition of cometary grains. Recent progress in laboratory studies of interplanetary dust particles (IDPs) complement the comet data, allowing inferences about the mineralogy and physical structure of the comet dust to be drawn from the observed elemental composition and infrared spectra. The in situ dust composition measurements at Halley, the composition of IDPs and their relation to comet dust, and the origin of the 3.4 micron hydrocarbon feature is discussed. Related discussion is also presented on aromatic components in comets and the 3.4 micron feature. These topics are briefly summarized.

Gehrz, R. D.↗
NASA NTRS1988

A two component model for thermal emission from organic grains in Comet Halley

Observations of Comet Halley in the near infrared reveal a triple-peaked emission feature near 3.4 micrometer, characteristic of C-H stretching in hydrocarbons. A variety of plausible cometary materials exhibit these features, including the organic residue of irradiated candidate cometary ices (such as the residue of irradiated methane ice clathrate, and polycyclic aromatic hydrocarbons. Indeed, any molecule containing -CH3 and -CH2 alkanes will emit at 3.4 micrometer under suitable conditions. Therefore tentative identifications must rest on additional evidence, including a plausible account of the origins of the organic material, a plausible model for the infrared emission of this material, and a demonstration that this conjunction of material and model not only matches the 3 to 4 micrometer spectrum, but also does not yield additional emission features where none is observed. In the case of the residue of irradiated low occupancy methane ice clathrate, it is argued that the lab synthesis of the organic residue well simulates the radiation processing experienced by Comet Halley.

Chyba, Christopher↗
NASA NTRS1988

Polyphenylquinoxalines containing alkylenedioxy groups

New polyphenylquinoxalines have been prepared from the reaction of novel bis(a-diketones) with aromatic bis(o-diamines). These polyphenylquinoxalines have lower glass transition temperatures and melt viscosities and consequently better processability than known polyphenylquinoxalines. The properties of these new polyphenylquinoxalines (tensile strength, modulus, elongation, adhesive strength, facture energy, and solvent resistance) are comparable with the properties known polyphenylquinoxalines.

Paul M Hergenrother↗
NASA NTRS1988

The link between IRAS spectra and near-infrared emission features in external galaxies

The relationship in external galaxies between the presence of the near-infrared (NIR) emission features attributed to polycyclic aromatic hydrocarbon (PAH) molecules, and the far-infrared (FIR) properties as observed by IRAS, is investigated. It is found that whenever the NIR features are absent in a galaxy, the FIR spectrum displays an enhancement at shorter wavelengths relative to normal galaxies. This enhancement is always associated with a strong activity in the galactic nucleus. Some Seyfert galaxies do not exhibit such an infrared signature and therefore they are probably energetically dominated by star-formation processes. Finally, the importance of hard UV photons and of the hot medium in the narrow line region of active nuclei is emphasized in relation to the survival of the PAH molecules. In this frame, the absence of PAHs in the galactic center could be taken as evidence for the presence of an active nucleus.

Desert, F. X.↗
NASA NTRS1988

Soluble and colorless polyimides

Results are reported in the form of reaction diagrams, graphs, and tables of research being conducted to synthesize and characterize linear aromatic polyimides which are soluble in common organic solvents and optically transparent in the 400-600 nm spectral range. These flexible and high-temperature polymeric films and coatings are needed for specific applications on space components such as antennas, solar cells, and thermal control coating systems. Several series of these polyimide films have been produced by making variations in the polymer molecular structure aimed at reducing the electronic interactions between the polymer chains.

St. Clair, Anne K.↗