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At least 1,099 records · Page 61

The Organic Component of Interstellar Dust

The distribution, chemical structure, and formation of organic matter in the interstellar medium are important to our understanding of the overall evolution of dust. The exchange of dust between the dense and diffuse interstellar medium, and the effects of processing on dust within dense clouds will affect the inventory of material available for incorporation into newly forming star and planetary systems. Observational ground-based studies have confirmed the widespread distribution of the 3.4 pm absorption band attributed to aliphatic hydrocarbons in the diffuse interstellar medium of our own galaxy, and in the dusty spectra of a few nearby galaxies, while space based observations from IS0 probed the signatures of corresponding mid-infrared features. Laboratory experiments which utilize both thermal processes and energetic processing by high energy photons and cosmic rays, produce candidate materials which offer close matches to the observed diffuse interstellar medium and extragalactic hydrocarbon absorption features. Through an analysis of the 4000 to 1000 cm (2.5 to 10 micrometers) region of the spectrum of diffuse interstellar medium (DISM) dust compared with the spectra of thirteen chemical entities produced in the laboratory which serve as analogs to the interstellar material, significant constraints have been placed on the applicability of proposed candidate materials to explain the interstellar features. The results indicate that the organic refractory material in the diffuse interstellar medium is predominantly hydrocarbon in nature, possessing little nitrogen or oxygen, with the carbon distributed between the aromatic and aliphatic forms. Long alkane chains H3C-(CH2),- with n much greater than 4 or 5 are not major constituents of this material. Comparisons to laboratory analogs indicate the DISM organic material resembles plasma processed pure hydrocarbon residues much more so than energetically processed ice residues. This result is consistent with a birthsite for the carrier of the 3.4 micrometers band in the outflow region of evolved carbon stars. Comparisons of dust from our own galaxy with that of distant galaxies suggests that the organic component of interstellar dust is widespread and may be an important universal reservoir of prebiotic organic carbon.

Pendleton, Yvonne↗

Composition of the Chandra ACIS Contaminant

The Advanced CCD Imaging Spectrometer (ACIS) on the Chandra X-ray Observatory is suffering a gradual loss of low energy sensitivity due to a buildup of a contaminant. High resolution spectra of bright astrophysical sources using the Chandra Low Energy Transmission Grating Spectrometer (LETGS) have been analyzed in order to determine the nature of the contaminant by measuring the absorption edges. The dominant element in the contaminant is carbon. Edges due to oxygen and fluorine are also detectable. We can place stringent limits on nitrogen and high Z elements such as AI, Si, and Mg. Not including H, we find that C, O, and F comprise less than 80%, 7%, and 7% of the contaminant by number, respectively, Nitrogen is less than 3% of the contaminant. We will assess various candidates for the contaminating material and the time dependence. For example, the detailed structure of the absorption edges provides information about the bonding structure of the compound, eliminating aromatic hydrocarbons as the contaminating material.

Marshall, Herman↗

Approaches to Establishing the Chemical Structure of Extraterrestrial Organic Solids

The majority of extraterrestrial organic matter in carbonaceous chondrites resides in a chemically complex, insoluble and perhaps macromolecular phase. We have been applying a series of independent solid state NMR experiments that are designed to provide a self consistent chemical characterization of this complex material. To date we have thoroughly analyzed 8 organic residues from different meteorites, including a CR2 (EET92042), CIl(Orgueil), CM2 (Murchison), Tagish Lake, CM2 (AlH83100), CM2 (Cold Bokkefeld), CM2 (Mighei), CM3 (Y86720). In fig 1. (1)H to (13)C cross polarization NMR spectra of four of these are shown. Note that there exists an enormous range in chemistry exhibited in organic solid [evident by the breadth of the spectral features both in the aliphatic region (sp(sup 3)) and the aromatic region (sp(sup 2))]. There is also considerable differences in the carbon chemistry across the meteorite groups.

Cody, G. D.↗

A New Antibody for Category 1 Biomarker Detection

At least two questions arise in developing a life-detection strategy: What do we look for and what will positive detection tell us? Unfortunately, many 'biomarkers' are not conclusive markers of biology. For example, sugars, amino acids, polycyclic aromatic hydrocarbons (PAH) and certain bacteria-like morphologies can all be produced non-biologically. Inferences of life following the detection of several inconclusive biomarkers in one sample will always be questioned. Although DNA, RNA and proteins are excellent markers of biology, and preserved on Earth for several millions of years, their survival over longer periods of time is low. Ideally, we should target biomarkers which are both stable over time and formed exclusively from biological processes, i.e. a 'category 1' biomarker under the new classification system of Mckay. We have used antibodies to detect category 1 and other biomarkers in rock samples. Extraction takes a few minutes and analysis a few hours. We have presented use of new antibodies to detect hopanes and have shown proof of operation during martian gravity.

Maule, J.↗

Research in Computational Astrobiology

We report on several projects in the field of computational astrobiology, which is devoted to advancing our understanding of the origin, evolution and distribution of life in the Universe using theoretical and computational tools. Research projects included modifying existing computer simulation codes to use efficient, multiple time step algorithms, statistical methods for analysis of astrophysical data via optimal partitioning methods, electronic structure calculations on water-nuclei acid complexes, incorporation of structural information into genomic sequence analysis methods and calculations of shock-induced formation of polycylic aromatic hydrocarbon compounds.

Chaban, Galina↗

Bisadducts from the Diels-Alder Trapping of Bis(o-Xylenols) Photochemically Generated from 2,5-Dibenzoyl-p-xylene

Photolysis of 2,5-dibenzoyl-p-xylene produces two discrete o-xylenols which undergo Diels-Alder cycloadditions with standard dienophiles, such as methyl acrylate, to produce 1,5-dihydroxy-1,5-diphenyl-l,2,3,4,5,6,7,8-octahydroanthracenes, 2a, in good yield (greater than 80%). The anti bisadduct crystallizes into hydrogen bonded stacks. Conversion of both syn- and anti-bisadducts to the corresponding anthracenes was achieved through the use of standard dehydration and aromatization chemistry.

Meador, Michael A.↗

Electrical Charging of the Clouds of Titan

We have used recent data on graphitic cloud particles in the atmosphere or Titan to compute the electrical charging of the particles (radii ranging from 0.01 microns to 0.26 microns). The charging on the nightside was rather similar to that obtained earlier (Borucki et al, Icarus, 72, 604-622, 1987) except that charge distributions on the particles are now computed and recently obtained cloud particle sizes and density distributions were employed. The negative charge on particles of 0.26 microns peaked at 9 at 150 km altitude. The computations were repeated for the dayside with the addition of photoelectron emission by the particles as a result of the absorption of solar UV radiation. Particles (except the very smallest) now became positively charged with particles of radius 0.26 microns being charged up to +47. Next, very small particles (radii approximately 3 x 10^-4 microns) of polycyclic aromatic hydrocarbons (PAHs) were introduced and treated as sources of negative ions since they could be either neutral or carry one negative charge. Moreover, they are mobile so that they had to be treated like molecular size negative ions although much more massive. They had the effect of substantially reducing the electron densities in the altitude range 190 to 310 km to values less than the negative PAH densities and increasing the peak electron charge on the larger particles. Particles of radius 0.26 microns bore peak charges of plus or minus 47 at altitudes of approximately 250 km. The simulated effect of PAHs on the nightside proved to be much less pronounced; at the peak negative PAH density, it was less than the electron density. The physics governing these results will be discussed.

Borucki, William J.↗

Lunar and Planetary Science XXXV: Organics and Alteration in Carbonaceous Chondrites: Goop and Crud

The session "Organics and Alteration in Carbonaceous Chondrites: Goop and Crud" included the following reports:Organics on Fe-Silicate Grains: Potential Mimicry of Meteoritic Processes?; Molecular and Compound-Specific Isotopic Study of Monocarboxylic Acids in Murchison and Antarctic Meteorites; Nanoglobules, Macromolecular Materials, and Carbon Sulfides in Carbonaceous Chondrites; Evidence for Terrestrial Organic Contamination of the Tagish Lake Meteorite; Nitrogen Isotopic Imaging of Tagish Lake Carbon Globules; Microscale Distribution of Hydrogen Isotopes in Two Carbonaceous Chondrites; The Nature and Origin of Aromatic Organic Matter in the Tagish Lake Meteorite; Terrestrial Alteration of CM Chondritic Carbonate; Serpentine Nanotubes in CM Chondrites; Experimental Study of Serpentinization Reactions; Chondrule Glass Alteration in Type IIA Chondrules in the CR2 Chondrites EET 87770 and EET 92105: Insights into Elemental Exchange Between Chondrules and Matrices; Aqueous Alteration of Carbonaceous Chondrites: New Insights from Comparative Studies of Two Unbrecciated CM2 Chondrites, Y 791198 and ALH 81002 ;and A Unique Style of Alteration of Iron-Nickel Metal in WIS91600, an Unusual C2 Carbonaceous Chondrite.

Source record↗

Lunar and Planetary Science XXXV: Astrobiology

The presentations in this session are: 1. A Prototype Life Detection Chip 2. The Geology of Atlantis Basin, Mars, and Its Astrobiological Interest 3. Collecting Bacteria Together with Aerosols in the Martian Atmosphere by the FOELDIX Experimental Instrument Developed with a Nutrient Detector Pattern: Model Measurements of Effectivity 4. 2D and 3D X-ray Imaging of Microorganisms in Meteorites Using Complexity Analysis to Distinguish Field Images of Stromatoloids from Surrounding Rock Matrix in 3.45 Ga Strelley Pool Chert, Western Australia 4. Characterization of Two Isolates from Andean Lakes in Bolivia Short Time Scale Evolution of Microbiolites in Rapidly Receding Altiplanic Lakes: Learning How to Recognize Changing Signatures of Life 5. The Effect of Salts on Electrospray Ionization of Amino Acids in the Negative Mode 6. Determination of Aromatic Ring Number Using Multi-Channel Deep UV Native Fluorescence 7. Microbial D/H Fractionation in Extraterrestrial Materials: Application to Micrometeorites and Mars 8. Carbon Isotope Characteristics of Spring-fed Iron-precipitating Microbial Mats 9. Amino Acid Survival Under Ambient Martian Surface UV Lighting Extraction of Organic Molecules from Terrestrial Material: Quantitative Yields from Heat and Water Extractions 10. Laboratory Detection and Analysis of Organic Compounds in Rocks Using HPLC and XRD Methods 11. Thermal Decomposition of Siderite-Pyrite Assemblages: Implications for Sulfide Mineralogy in Martian Meteorite ALH84001 Carbonate Globules 12. Determination of the Three-Dimensional Morphology of ALH84001 and Biogenic MV-1 Magnetite: Comparison of Results from Electron Tomography and Classical Transmission Electron Microscopy 13. On the Possibility of a Crypto-Biotic Crust on Mars Based on Northern and Southern Ringed Polar Dune Spots 14. Comparative Planetology of the Terrestrial Inner Planets: Implications for Astrobiology 15. A Possible Europa Exobiology 16. A Possible Biogeochemical Model for Titan

Source record↗

Electrical Charging of Aerosols and Conductivity of Titan's Atmosphere

We have used recent data on graphitic cloud particles in the atmosphere of Titan to compute the electrical charging of the particles (radii ranging from 0.01 microns to 0.26 microns). The charging on the nightside was rather similar to that obtained earlier except that charge distributions on the particles are now computed and recently obtained cloud particle sizes and density distributions were employed. The negative charge on particles of 0.26 microns peaked at 9 at 150 km altitude. The computations were repeated for the dayside with the addition of photoelectron emission by the particles as a result of the absorption of solar UV radiation. Particles (except the very smallest) now became positively charged with particles of radius 0.26 microns being charged up to +47. Next, very small particles (radii approx. 3 x 10 (sup -4) microns) of polycyclic aromatic hydrocarbons (PAHs) were introduced and treated as sources of negative ions since they could be either neutral or carry one negative charge. Moreover, they are mobile so that they had to be treated like molecular size negative ions although much more massive. They had the effect of substantially reducing the electron densities in the altitude range 190 to 310 km to values less than the negative PAH densities and increasing the peak electron charge on the larger particles. Particles of radius 0.26 microns bore peak charges of approx. +47 at altitudes of approx. 250 km. The simulated effect of PAHs on the nightside proved to be much less pronounced; at the peak negative PAH density, it was less than the electron density. The physics governing these results will be discussed.

Borucki, W. J.↗

Flame Retardant Epoxy Resins

As part of a program to develop fire resistant exterior composite structures for future subsonic commercial aircraft, flame retardant epoxy resins are under investigation. Epoxies and their curing agents (aromatic diamines) containing phosphorus were synthesized and used to prepare epoxy formulations. Phosphorus was incorporated within the backbone of the epoxy resin and not used as an additive. The resulting cured epoxies were characterized by thermogravimetric analysis, propane torch test, elemental analysis and microscale combustion calorimetry. Several formulations showed excellent flame retardation with phosphorous contents as low as 1.5% by weight. The fracture toughness of plaques of several cured formulations was determined on single-edge notched bend specimens. The chemistry and properties of these new epoxy formulations are discussed.

Thompson, C. M.↗

Interstellar Dust Models Consistent with Extinction, Emission, and Abundance Constraints

We present new interstellar dust models which have been derived by simultaneously fitting the far ultraviolet to near infrared extinction, the diffuse infrared emission, and, unlike previous models, the elemental abundances in dust for the diffuse interstellar medium. We found that dust models consisting of a mixture of spherical graphite and silicate grains, polycyclic aromatic hydrocarbon (PAH) molecules, in addition to porous composite particles containing silicate, organic refractory, and water ice, provide an improved .t to the UV-to-infrared extinction and infrared emission measurements, while consuming the amounts of elements well within the uncertainties of adopted interstellar abundances, including B star abundances. These models are a signi.cant improvement over the recent Li & Draine (2001, ApJ, 554, 778) model which requires an excessive amount of silicon to be locked up in dust: 48 ppm (atoms per million of H atoms), considerably more than the solar abundance of 34 ppm or the B star abundance of 19 ppm.

Zubko, Viktor↗

Organic-Inorganic Hybrids Using Novel Phenylethynyl Imide Silanes

In this presentation, polyimide-silica hybrids using novel phenylethynyl imide silanes are reported. The phenylethynyl group is present in the organic precursor as either a pendent or an end group to bond chemically with the polyimide adhesive containing phenylethynyl groups during processing, while the silane group of the organic precursor would chemically react with the inorganic precursor through oxane bond formation. The chemical compositions of these novel hybrids were examined using X-ray mapping modes of scanning electron microscopy (SEM), which revealed a silicon gradient interphase between the high surface energy substrate and the polyimide adhesive. Novel aromatic phenylethynyl imide silanes (APEISs) and pendent phenylethynyl imide oligomeric disilanes (PPEIDSs) have been synthesized, and sol-gel solutions containing the new silanes, a phenylethynyl terminated imide oligomer (PETI-5), and an inorganic precursor were formulated to develop a gradient hybrid interphase between a titanium alloy and the adhesive. Two different sol-gel systems were investigated to develop organic-inorganic hybrids. Hybrid I was composed of an organic precursor containing both phenylethynyl and silane groups (PPEIDS) and an inorganic precursor. Functional group concentrations were controlled by the variation of the molecular weight of the imide backbone of PPEIDS. Hybrid II was composed of organic and inorganic precursors and a coupling agent containing both phenylethynyl and silane groups. Morphology and chemical composition of the hybrid interphase between the inorganic substrate and the adhesive were investigated, and the bond strength and durability were evaluated using lap shear tests at various conditions. The assessment of how the bonding at an interface is affected by various sol-gel solution compositions and environments is reported.

Park, C.↗

Tholins as Coloring Agents on Solar System Bodies

Pre-biotic organic materials appear to be common on many small bodies in the outer Solar System, as evidenced by the color properties of these objects. We report on our continuing study of color properties in connection with the presence of complex organic solids (tholins) among the planets and their satellites, the asteroids, and the trans- Neptunian objects (Kuiper Belt objects). Most small, icy bodies in the Solar System, whether they have high or low surface reflectance (albedo), show a pronounced downward slope in reflectance at wavelengths shorter than approx. 1 micron. This increasing absorption of sunlight toward shorter wavelengths is characteristic of pi-bonds in hydrocarbons having chains or rings of conjugated C atoms. Tholins, which contain polycyclic aromatic and aliphatic hydrocarbons, exhibit these color properties. Using the complex refractive indices of tholins in models of the reflectance spectra of icy bodies in the Solar System, we find that these complex organic materials satisfactorily account for the coloration so widely observed. The new results presented here show that the wide variety of colors of Kuiper Belt objects can be fit very well with tholins, as can the colors of Pluto and Triton. The implications of these fits of Kuiper Belt objects is that complex organic material is created on their surfaces by energetic particle bombardment of native ices, and also may be accreted from external sources. In the cases of Pluto and Triton, photochemistry of their weak N2 + CH4 + CO atmospheres produces complex organic molecules that precipitate to the surface, providing local color.

Cruikshank, D. P.↗

Mid and Near-IR Absorption Spectra of PAH Neutrals and Ions in H20 Ice to Facilitate their Astronomical Detection

Polycyclic aromatic hydrocarbons (PAHs) are believed to be the most abundant and widespread class of organic compounds in the universe, having been observed in emission towards energetic regions and absorption towards colder ones.We will present IR spectra of PAHs and their cations in H20 ice measured in the laboratory in the hopes that this will facilitate the detection of these features in the interstellar medium.

Bernstein, Max P.↗

Crystal structures of pinoresinol-lariciresinol and phenylcoumaran benzylic ether reductases and their relationship to isoflavone reductases

Despite the importance of plant lignans and isoflavonoids in human health protection (e.g. for both treatment and prevention of onset of various cancers) as well as in plant biology (e.g. in defense functions and in heartwood development), systematic studies on the enzymes involved in their biosynthesis have only recently begun. In this investigation, three NADPH-dependent aromatic alcohol reductases were comprehensively studied, namely pinoresinol-lariciresinol reductase (PLR), phenylcoumaran benzylic ether reductase (PCBER), and isoflavone reductase (IFR), which are involved in central steps to the various important bioactive lignans and isoflavonoids. Of particular interest was in determining how differing regio- and enantiospecificities are achieved with the different enzymes, despite each apparently going through similar enone intermediates. Initially, the three-dimensional x-ray crystal structures of both PLR_Tp1 and PCBER_Pt1 were solved and refined to 2.5 and 2.2 A resolutions, respectively. Not only do they share high gene sequence similarity, but their structures are similar, having a continuous alpha/beta NADPH-binding domain and a smaller substrate-binding domain. IFR (whose crystal structure is not yet obtained) was also compared (modeled) with PLR and PCBER and was deduced to have the same overall basic structure. The basis for the distinct enantio-specific and regio-specific reactions of PCBER, PLR, and IFR, as well as the reaction mechanism and participating residues involved (as identified by site-directed mutagenesis), are discussed.

NASA Discipline Plant Biology↗

Single photon infrared emission spectroscopy: a study of IR emission from UV laser excited PAHs between 3 and 15 micrometers

Single-photon infrared emission spectroscopy (SPIRES) has been used to measure emission spectra from polycyclic aromatic hydrocarbons (PAHs). A supersonic free-jet expansion has been used to provide emission spectra of rotationally cold and vibrationally excited naphthalene and benzene. Under these conditions, the observed width of the 3.3-micrometers (C-H stretch) band resembles the bandwidths observed in experiments in which emission is observed from naphthalene with higher rotational energy. To obtain complete coverage of IR wavelengths relevant to the unidentified infrared bands (UIRs), UV laser-induced desorption was used to generate gas-phase highly excited PAHs. Lorentzian band shapes were convoluted with the monochromator-slit function in order to determine the widths of PAH emission bands under astrophysically relevant conditions. Bandwidths were also extracted from bands consisting of multiple normal modes blended together. These parameters are grouped according to the functional groups mostly involved in the vibration, and mean bandwidths are obtained. These bandwidths are larger than the widths of the corresponding UIR bands. However, when the comparison is limited to the largest PAHs studied, the bandwidths are slightly smaller than the corresponding UIR bands. These parameters can be used to model emission spectra from PAH cations and cations of larger PAHs, which are better candidate carriers of the UIRs.

Non-NASA Center↗

Atmospheric H2O2 measurement: comparison of cold trap method with impinger bubbling method

Collection of atmospheric H2O2 was performed by a cold trap method using dry ice-acetone as the refrigerant. The air was drawn by a pump into a glass gas trap immersed in the dry ice-acetone slush in a dewar flask at a flow rate of 2.5 l min-1 for approximately 2 h. Collection efficiency was > 99% and negligible interferences by O3, SO2 or organic matter with the collected H2O2 in the trap were observed. This method was compared with the air impinger bubbling method which has been previously described (Kok et al., 1978a, b, Envir. Sci. Technol. 12, 1072-1080). The measured total peroxide (H2O2 + organic peroxide) values in a series of aim samples collected by the impinger bubbling method (0.06-3.7 ppb) were always higher than those obtained by the cold trap method (0.02-1.2 ppb). Laboratory experiments suggest that the difference in values between the two methods probably results from the aqueous phase generation of H2O2 and organic peroxide in the impinger solution by a reaction of atmospheric O3 with olefinic and aromatic compounds. If these O3-organic compound reactions which occur in the impinger also occur in aqueous droplets in the atmosphere, the process could be very important for aqueous phase generation of H2O2 in clouds and rainwater.

NASA Discipline Exobiology↗