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At least 397 records · Page 22
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

The Identification of Complex Organic Molecules in the Interstellar Medium: Using Lasers and Matrix Isolation Spectroscopy to Simulate the Interstellar Environment

The Astrochemistry Group at NASA Ames Research Center is interested in the identification of large organic molecules in the interstellar medium Many smaller organic species (e.g. hydrocarbons, alcohols, etc.) have been previously identified by their radiofrequency signature due to molecular rotations. However, this becomes increasingly difficult to observe as the size of the molecule increases. Our group in interested in the identification of the carriers of the Diffuse Interstellar Bands (absorption features observed throughout the visible and near-infrared in the spectra of stars, due to species in the interstellar medium). Polycyclic Aromatic Hydrocarbons (PAHs) and related molecules are thought to be good candidates for these carriers. Laboratory experiments am performed at Ames to simulate the interstellar environment, and to compare spectra obtained from molecules in the laboratory to those derived astronomically. We are also interested in PAHs with respect to their possible connection to the UIR (Unidentified infrared) and ERE (Extended Red Emission) bands - emission features found to emanate from particular regions of our galaxy (e.g. Orion nebula, Red Rectangle, etc.). An old, "tried and proven spectroscopic technique, matrix isolation spectroscopy creates molecular conditions ideal for performing laboratory astrophysics.

Stone, Bradley M.↗
NASA NTRS2000

Soil, Groundwater, Surface Water, and Sediments of Kennedy Space Center, Florida: Background Chemical and Physical Characteristics

This study documented background chemical composition of soils, groundwater, surface; water, and sediments of Kennedy Space Center. Two hundred soil samples were collected, 20 each in 10 soil classes. Fifty-one groundwater wells were installed in 4 subaquifers of the Surficial Aquifer and sampled; there were 24 shallow, 16 intermediate, and 11 deep wells. Forty surface water and sediment samples were collected in major watershed basins. All samples were away from sites of known contamination. Samples were analyzed for organochlorine pesticides, aroclors, chlorinated herbicides, polycyclic aromatic hydrocarbons (PAH), total metals, and other parameters. All aroclors (6) were below detection in all media. Some organochlorine pesticides were detected at very low frequencies in soil, sediment, and surface water. Chlorinated herbicides were detected at very low frequencies in soil and sediments. PAH occurred in low frequencies in soiL, shallow groundwater, surface water, and sediments. Concentrations of some metals differed among soil classes, with subaquifers and depths, and among watershed basins for surface water but not sediments. Most of the variation in metal concentrations was natural, but agriculture had increased Cr, Cu, Mn, and Zn.

Shmalzer, Paul A.↗
NASA NTRS2000

Ultraviolet Irradiation of Naphthalene in H2O Ice: Implications for Meteorites and Biogenesis

The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H2O ice under astrophysical conditions, and the products were analyzed using infrared spectroscopy and high performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H2O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry of the reactions is described and leads to specific predictions of the relative abundances of various oxidized naphthalenes that should exist in meteorites if interstellar ice photochemistry influenced their aromatic inventory. Since oxidized PAHs are present in carbon-rich meteorites and interplanetary dust particles (IDPs), and ubiquitous in and fundamental to biochemistry, the delivery of such extraterrestrial molecules to the early Earth may have played a role in the origin and evolution of life.

Bernstein, Max P.↗
NASA NTRS2001

Visualization of Microbial Biomarkers by Scanning Electron Microscopy

We are developing tools to link the biochemical structure of selected biomarkers with putative biogenic structures observed in mineralized samples. The detection of evidence of life on Mars and other planets will rely on methods that can discriminate compounds formed exclusively by living organisms. While biogenic compounds, such as amino acids and nucleotides have been discovered in extraterrestrial sources, such as meteorites and comets, their formation can be explained by abiotic means. The formation of cellular structures, or more elaborate organic molecules, such as complex lipids, proteins or nucleic acids, however, is strongly correlated to the presence of even the most primitive life processes. Recent evidence lends support to the hypothesis that life may have once existed on Mars. Carbonate globules and ppm concentrations of polycyclic aromatic hydrocarbons (PAHs) have been described in ALH84001, a meteorite originating from Mars ejecta captured by Earth over 13,000 years ago. The localized high concentration of PAHs that follow an increasing gradient from the intact fusion crust towards the interior corresponds to microgram quantities of hydrocarbon. Even though ALH84001 and other similar meteorites have withstood the forces capable of ejecting rock through Mars' escape velocity, upon entering Earth's atmosphere, their core temperatures are likely not to have been raised significantly, as evidenced by the survival of remanent magnetic signatures. Ideal biomarkers of ancient or modern biological life would include molecules that are (or were) pervasive and highly resistant to degradation. Also, requisite methods of detection should be simple, extremely sensitive and broadly inclusive (NASA SP-530). Lipopolysaccharide (LPS), peptidoglycan or pseudopeptidoglycan and beta-glucan are microbial cell wall components which together cover the entire microbial spectrum of eubacteria, archea and fungi. They are all remarkably resistant to thermal degradation. Fortunately, many antimicrobial defense systems of higher organisms require sensitive detection to combat microbial pathogens. We employ here the primitive immune system of the evolutionarily ancient horseshoe crab, Limulus polyphemus. This species relies on multi-enzyme signal amplification detection of cell wall molecules and they can be applied to the development of useful detectors of life. An extension of this work includes the visualization of microbial signatures by labeling LAL components with chromogenic or electron dense markers. The protein Limulus Anti-LPS Factor (LALF) has an extremely high affinity for LPS. By coupling LALF binding with colloidal gold labels we demonstrate a correlation of the structures visible by electron microscopy with biochemical evidence of microbial cell wall materials. Pure silica particles were mixed with cultures of E. coli (10(exp 6) cfu/mL). Samples were washed sequentially with buffered saline, LALF, antibody to LALF and finally colloidal gold-labeled Protein A. Negative controls were not exposed to E. coli but received identical treatment otherwise. Samples were coated with carbon and imaged on a JEOL JSM-840 scanning electron microscope with LaB6 source in the back scatter mode with the JEOL annular back scatter detector. 20 nm-scale black spots in this contrast-reversed image originate from electrons back-scattered by gold atoms. Negative controls did not give any signal. Future work will expand application of this technique to soil simulants and mineralized rock samples.

Wainwright, Norman R.↗
NASA NTRS1994

Characterization of the Minimum Energy Paths for the Reactions of CH(X(sup 2 Pi) and (1)CH2 with C2H2

The reactions of CH(sup 2 Pi) and singlet methylene (1)CH2 with acetylene lead to intermediates which may be important in soot formation. CH(sup 2 Pi) + acetylene leads to CHCHCH (C3H3), CHCCH (C3H2), and propargyl (CH2CCH). (1)CH2 + acetylene leads to cyclopropene and propargyl. All of these reaction products are formed with no barrier. Miller and Melius have previously discussed the dimerization of propargyl to give benzene. C3H3 and C3H2 can dimerize with no barrier to give benzene and para-benzyne, respectively. C3H3 and C3H2 can also add to smaller polynuclear aromatic hydrocarbons (PAH), and may be important species in forming larger PAH or fullerenes.

Walch, Stephen P.↗
NASA NTRS2001

The Production of Complex Organics from Interstellar Ices

Infrared spectroscopy of ices in interstellar dense molecular clouds has shown that they contain a variety of simple molecules, as well as aromatic hydrocarbons. While in these clouds, these ices are processed by ultraviolet light and cosmic rays. High vacuum, UV irradiation laboratory simulations conducted using various realistic approx. 10 K interstellar mixed-molecular ice analogs, both with and without polycyclic aromatic hydrocarbons (PAHs), have been carried out in NASA-Ames' Astrochemistry Laboratory. Upon warming, these irradiated ices are found to produce refractory organic residues. These residues have been analyzed using a variety of techniques, including HPLC and laser desorption mass spectrometry, and they have been shown to contain a variety of complex organic compounds. Several of these compounds may be of prebiotic significance. In particular, we will discuss the detection of quinones (substituted PAHs that are used by living systems for electron transport) and amphiphiles (molecules that self-assemble to form membranes). Laboratory simulations have also demonstrated that the organic products can show isotopic enrichments in D that provide clues for the mechanisms of their formation. Similar compounds and D enrichments are seen in the organics found in primitive meteorites, suggesting a direct link between interstellar chemistry and the delivery of organics to newly formed planets.

Sandford, Scott A.↗
NASA NTRS1997

Characteristics of Interstellar and Circumstellar Dust

This paper will review our current knowledge of circumstellar and interstellar dust from an astronomical point of view. About half of the interstellar dust volume consists of amorphous silicates. The remainder has to be made up of an carbonaceous component such as graphite, amorphous carbon (i.e., soot), Polycyclic Aromatic Hydrocarbon molecules (PAHs), and/or organic grain mantles (i.e., mixed polymers). The observational evidence for these components will be reviewed and their relative importance assessed. The emphasis will be on recent observations using the Infrared Space Observatory. Most of these dust components are formed in the outflows from stars in the late stages of their evolution (i.e., red giants, planetary nebulae, novae, supergiants, Wolf Rayet stars, and supernovae). Indeed, observation of such objects indicate an even richer spectrum of stardust components, including also SiC, MgS, and aluminates and crystalline silicates. These observations will be briefly discussed. The stardust budget of the galaxy will be reviewed and the relative importance of the various birth sites assessed. Finally, in recent years, isotopic composition studies have shown that some circumstellar and interstellar dust grains have been incorporated into solar system bodies such as planetary dust particles and meteorites without totally losing their identity. Among the components identified are SiC, graphite, diamonds, PAHs, aluminum oxides, as well as various trace element carbides. Studies of this kind have opened up a new window on the composition and structure of interstellar dust. These different sources of information on interstellar and circumstellar dust will be briefly contrasted.

Tielens, A. G. G. M.↗
NASA NTRS1997

Spectrophotometry of Dust in Comet Hale-Bopp

Comets, such as Hale-Bopp (C/1995 O1), are frozen reservoirs of primitive solar nebula dust grains and ices. Analysis of the composition of cometary dust grains from infrared spectroscopic techniques permits an estimation of the types of organic and inorganic materials that constituted the early primitive solar nebula. In addition, the cometary bombardment of the Earth (approximately 3.5 Gy ago) supplied the water for the oceans and brought organic materials to Earth which may have been biogenic. Spectroscopic observations of comet Hale-Bopp suggest the possible presence of organic hydrocarbon species, silicate and olivine dust grains, and water ice. Spectroscopy near 3 microns obtained in Nov 1996 r=2.393 AU, delta=3.034 AU) shows a feature which we attribute to PAH emission. The spatial morphology of the 3.28 microns PAH feature is also presented. Optical and infrared spectrophotometric observations of comets convey valuable information about the spatial distribution and properties of dust and gas within the inner coma. In the optical and NIR shortward of 2 microns, the observed light is primarily scattered sunlight from the dust grains. At longer wavelengths, particularly in the 10 gm window, thermal emission from these grains dominates the radiation allowing an accurate estimate of grain sizes and chemical composition. Here we present an initial analysis of spectra taken with the NASA HIFOGS at 7-14 microns as part of a multiwavelength temporal study of the "comet of the century".

Witteborn, Fred C.↗
NASA NTRS2002

Website for the Astrochemistry Laboratory, Astrophysics Branch, Space Sciences Division

The Astrochemistry Laboratory in the Astrophysics Branch (SSA) of the Space Sciences Division at NASA's Ames Research Center specializes in the study of extraterrestrial materials and their analogs. The staff has pioneered laboratory studies of space environments including interstellar, cometary, and planetary ices, simulations of the so-called 'Unidentified' Infrared Emission Bands and Diffuse Interstellar Bands using PAHs (Polycyclic Aromatic Hydrocarbons) and PAH-related materials, and has extensive experience with low-temperature spectroscopy and astronomical observation. Important discoveries made by the Astrochemistry Group include: (1) The recognition that polycyclic aromatic hydrocarbons and their ions are common in space; (2) The identification of a major fraction of the known molecular species frozen in interstellar/pre-cometary ices; (3) The recognition that a significant fraction of the carbon in the interstellar medium is carried by both microdiamonds and organic materials; (4) The expansion of the types of molecules expected to be synthesized in interstellar/pre-cometary ices. These could be delivered to the early Earth (or other body) and influence the origin or early evolution of life.

Sandford, Scott↗
NASA NTRS2003

Wavelength Shifts of the 7.7 Micron Emission Band in Reflection Nebulae

Using spatial-spectral data cubes of reflection nebulae obtained by ISOCAM, we have observed a shift in the central wavelength of the 7.7 micron band within several reflection nebulae. The band shifts progressively from approx. 7.8 microns near the edge of the nebulae to approx. 7.6 microns towards the center of the nebulae. The ratio of the 11.3/7.7 micron bands also changes with distance from the central star, first rising from the center towards the edge of the nebula, then falling at the largest distances from the star, consistent with the 11.3/7.7 micron band ratio being controlled by the PAH ionization state. The behavior of the 7.7 micron band center can be explained either by assuming that anions are the origin of the 7.85 micron band and cations the 7.65 micron band, or that the band center wavelength depends on the chemical nature of the PAHs.

Bregman, Jesse↗
NASA NTRS2004

From Interstellar Polycyclic Aromatic Hydrocarbons and Ice to the Origin of Life

Tremendous strides have been made in our understanding of interstellar material over the past twenty years thanks to significant, parallel developments in observational astronomy and laboratory astrophysics. Twenty years ago the composition of interstellar dust was largely guessed at, the concept of ices in dense molecular clouds ignored, and the notion of large, abundant, gas phase, carbon rich molecules widespread throughout the interstellar medium (ISM) considered impossible. Today the composition of dust in the diffuse ISM is reasonably well constrained to cold refractory materials comprised of amorphous and crystalline silicates mixed with an amorphous carbonaceous material containing aromatic structural units and short, branched aliphatic chains. In the dense ISM, the birthplace of stars and planets, these cold dust particles are coated with mixed molecular ices whose composition is very well constrained. Lastly, the signature of carbon-rich polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by early interstellar chemistry standards, is widespread throughout the Universe. The first part of this talk will describe how infrared studies of interstellar space, combined with laboratory simulations, have revealed the composition of interstellar ices (the building blocks of comets) and the high abundance and nature of interstellar PAHs. The laboratory database has now enabled us to gain insight into the identities, abundances, and physical state of many interstellar materials. Within a dense molecular cloud, and especially in the presolar nebula, the materials frozen into the interstellar/precometary ices are photoprocessed by ultraviolet light and produce more complex molecules. The remainder of the presentation will focus on the photochemical evolution of these materials and the possible role of these compounds on the to the carbonaceous components of micrometeorites, they are likely to have been important sources of complex materials on the early Earth and their composition may be related to the origin of life.

Allamandola, Louis↗
NASA NTRS2004

Formation and Destruction Processes of Interstellar Dust: From Organic Molecules to carbonaceous Grains

The study of the formation and destruction processes of cosmic dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. interstellar dust presents a continuous size distribution from large molecules, radicals and ions to nanometer-sized particles to micron-sized grains. The lower end of the dust size distribution is thought to be responsible for the ubiquitous spectral features that are seen in emission in the IR (UIBs) and in absorption in the visible (DIBs). The higher end of the dust-size distribution is thought to be responsible for the continuum emission plateau that is seen in the IR and for the strong absorption seen in the interstellar UV extinction curve. All these spectral signatures are characteristic of cosmic organic materials that are ubiquitous and present in various forms from gas-phase molecules to solid-state grains. Although dust with all its components plays an important role in the evolution of interstellar chemistry and in the formation of organic molecules, little is known on the formation and destruction processes of dust. Recent space observations in the UV (HST) and in the IR (ISO) help place size constraints on the molecular component of carbonaceous IS dust and indicate that small (ie., subnanometer) PAHs cannot contribute significantly to the IS features in the UV and in the IR. Studies of large molecular and nano-sized IS dust analogs formed from PAH precursors have been performed in our laboratory under conditions that simulate diffuse ISM environments (the particles are cold -100 K vibrational energy, isolated in the gas phase and exposed to a high-energy discharge environment in a cold plasma). The species (molecules, molecular fragments, ions, nanoparticles, etc) formed in the pulsed discharge nozzle (PDN) plasma source are detected with a high-sensitivity cavity ring-down spectrometer (CRDS). We will present new experimental results that indicate that nanoparticles are generated in the plasma. From these unique measurements, we derive information on the nature, the size and the structure of interstellar dust particles, the growth and the destruction processes of IS dust and the resulting budget of extraterrestrial organic molecules.

Salama, F.↗
NASA NTRS2000

Laboratory investigation of the contribution of complex aromatic/aliphatic polycyclic hybrid molecular structures to interstellar ultraviolet extinction and infrared emission

We have demonstrated by experiment that, in an energetic environment, a simple polycyclic aromatic hydrocarbon (PAH) such as naphthalene will undergo chemical reactions that produce a wide array of more complex species (an aggregate). For a stellar wind of a highly evolved star (post-asymptotic giant branch [post-AGB]), this process would be in addition to what is expected from reactions occurring under thermodynamic equilibrium. A surprising result of that work was that produced in substantial abundance are hydrogenated forms that are hybrids of polycyclic aromatic and polycyclic alkanes. Infrared spectroscopy described here reveals a spectral character for these materials that has much in common with that observed for the constituents of circumstellar clouds of post-AGB stars. It can be demonstrated that a methylene (-CH2-) substructure, as in cycloalkanes, is the likely carrier of the 6.9 microns band emission of dust that has recently been formed around IRAS 22272+5433, NGC 7027, and CPD -56 8032. Ultraviolet spectroscopy previously done with a lower limit of 190 nm had revealed that this molecular aggregate can contribute to the interstellar extinction feature at 2175 angstroms. We have now extended our UV spectroscopy of these materials to 110 nm by a vacuum ultraviolet technique. That work, described here, reveals new spectral characteristics and describes how material newly formed during the late stages of stellar evolution could have produced an extinction feature claimed to exist at 1700 angstroms in the spectrum of HD 145502 and also how the newly formed hydrocarbon material would be transformed/aged in the general interstellar environment. The contribution of this molecular aggregate to the rise in interstellar extinction at wavelengths below 1500 angstroms is also examined. The panspectral measurements of the materials produced in the laboratory, using plasmas of H, He, N, and O to convert the simple PAH naphthalene to an aggregate of complex species, provide insight into possible molecular structure details of newly formed hydrocarbon-rich interstellar dust and its transformation into aged material that becomes resident in the interstellar medium. Specifically the presence of naphthalene-like and butadiene-like conjugated structures as chromophores for the 2175 angstroms ultraviolet extinction feature is indicated.

NASA Discipline Exobiology↗
NASA NTRS1997

A laboratory analog for the carrier of the 3 micron emission of the protoplanetary nebula IRAS 05341+0852

A mixture of the polycyclic aromatic hydrocarbons (PAHs), acenaphthylene and acenaphthene, when subjected to the energetic environment of a hydrogen plasma, is transformed into a material that exhibits an infrared absorption profile in the 3 micron region that is an excellent match of the protoplanetary nebula IRAS 05341+0852 emission profile in the same wavelength region. Acenaphthylene and acenaphthene were chosen as precursors in the experiment because these molecules have a structure that can be described as a keystone in a process in which carbon atoms in a stellar wind condense into PAH species. The spectral match between experiment and observations appears to validate that scenario.

Non-NASA Center↗
NASA NTRS1997

Experimental indication of a naphthalene-base molecular aggregate for the carrier of the 2175 angstroms interstellar extinction feature

Experiments where the simple polycyclic aromatic hydrocarbon (PAH) naphthalene (C10H8) is subjected to the energetic environment of a plasma have resulted in the synthesis of a molecular aggregate that has ultraviolet spectral characteristics that suggest it provides insight into the nature of the carrier of the 2175 angstroms interstellar extinction feature and may be a laboratory analog. Ultraviolet, visible, infrared, and mass spectroscopy, along with gas chromatography, indicate that it is a molecular aggregate in which an aromatic double ring ("naphthalene") structural base serves as the electron "box" chromophore that gives rise to the envelope of the 2175 angstroms feature. This chromophore can also provide the peak of the feature or function as a mantle in concert with another peak provider such as graphite. The molecular base/chromophore manifests itself both as a structural component of an alkyl-aromatic polymer and as a substructure of hydrogenated PAH species. Its spectral and molecular characteristics are consistent with what is generally expected for a complex molecular aggregate that has a role as an interstellar constituent.

NASA Discipline Exobiology↗
NASA NTRS1999

UV irradiation of polycyclic aromatic hydrocarbons in ices: production of alcohols, quinones, and ethers

Polycyclic aromatic hydrocarbons (PAHs) in water ice were exposed to ultraviolet (UV) radiation under astrophysical conditions, and the products were analyzed by infrared spectroscopy and mass spectrometry. Peripheral carbon atoms were oxidized, producing aromatic alcohols, ketones, and ethers, and reduced, producing partially hydrogenated aromatic hydrocarbons, molecules that account for the interstellar 3.4-micrometer emission feature. These classes of compounds are all present in carbonaceous meteorites. Hydrogen and deuterium atoms exchange readily between the PAHs and the ice, which may explain the deuterium enrichments found in certain meteoritic molecules. This work has important implications for extraterrestrial organics in biogenesis.

NASA Center ARC↗
NASA NTRS1998

The diffuse interstellar bands: a tracer for organics in the diffuse interstellar medium?

The diffuse interstellar bands (DIBs) are absorption bands seen in the spectra of stars obscured by interstellar dust. DIBs are recognized as a tracer for free, organic molecules in the diffuse interstellar medium (ISM). The potential molecular carriers for the DIBs are discussed with an emphasis on neutral and ionized polycyclic aromatic hydrocarbons (PAHs) for which the most focused effort has been made to date. From the combined astronomical, laboratory and theoretical study, it is concluded that a distribution of free neutral and ionized complex organics (PAHs, fullerenes, unsaturated hydrocarbons) represents the most promising class of candidates to account for the DIBs. The case for aromatic hydrocarbons appears particularly strong. The implied widespread distribution of complex organics in the diffuse ISM bears profound implications for our understanding of the chemical complexity of the ISM, the evolution of prebiotic molecules and its impact on the origin and the evolution of life on early Earth through the exogenous delivery (cometary encounters and metoritic bombardments) of prebiotic organics.

Biogenesis↗
NASA NTRS2004

Integration of a Micro-Chip Amino Acid Chirality Detector into the MOD Instrument Concept

The MOD (Mars Organic Detector) instrument concept consists of a sublimation apparatus for organic compound isolation connected to a microfabricated microfluidic analyzer containing a sipper, pumps and a separation channel for organic compound characterization. The target organic compounds are amino acids and polycyclic aromatic hydrocarbons (PAHs). Solid samples are placed within the sublimation apparatus and heated to release organic compounds which sublime onto a cold finger. Half of the cold finger is coated with fluorescamine. which reacts with amino acids and other primary amines to generate an intense fluorescent derivative while the other half is uncoated and is used to directly detect PAH fluorescence, A capillary sipper is then used to dissolve and sample the labeled amino acids and integrated microfabricated pumps transport the labeled amino acids to the chip for analysis. The sample is separated using capillary zone electrophoresis (CZE) together with chiral dextrins to determine amino acid composition and chirality. During the grant period, the following steps have been completed toward the development of a robust instrument and chemistry.

Bada, Jeffrey L.↗