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At least 217 records · Page 12

Ionized polycyclic aromatic hydrocarbons and the diffuse interstellar bands

A good case has recently been made that the unidentified infrared emission features arise from positively charged, partially hydrogenated polycyclic aromatic hydrocarbons (PAHs). In this letter it is suggested that these exceedingly stable ions are also the carriers of the diffuse interstellar bands. Although a large variety of PAH isomers is possible, the more condensed forms are substantially more stable than the less condensed forms and are expected to be dominant in the harsh interstellar environment. While neutral PAHs do not absorb in the visible, their ionized counterparts do. Because of their low ionization potential, a substantial fraction of the interstellar PAHs will be ionized. Visible spectra of the most stable PAH cations isolated in glasses are compared directly to the interstellar band spectra. Although the laboratory spectra are on an extremely compressed scale and solid state shifts are present, the comparison is favorable. Since little information is available concerning the spectroscopic properties of these species in the gas phase, a considerable amount of laboratory and theoretical work is called for to test this hypothesis.

Crawford, M. K.↗

Spatially resolved organic analysis of the Allende meteorite

The distribution of polycyclic aromatic hydrocarbons (PAHs) in the Allende meteorite has been probed with two-step laser desorption/laser multiphoton ionization mass spectrometry. This method allows direct in situ analysis with a spatial resolution of 1 sq mm or better of selected organic molecules. Spectra from freshly fractured interior surfaces of the meteorite show that PAH concentrations are locally high compared to the average concentrations found by wet chemical analysis of pulverized samples. The data suggest that the PAHs are primarily associated with the fine-grained matrix, where the organic polymer occurs. In addition, highly substituted PAH skeletons were observed. Interiors of individual chondrules were devoid of PAHs at the detection limit (about 0.05 ppm).

Zenobi, Renato↗

Spectral structure near the 11.3 micron emission feature

If the 11.3 micron emission feature seen in the spectra of many planetary nebulae, H II regions, and reflection nebulae is attributable to polycyclic aromatic hydrocarbons (PAHs), then additional features should be present between 11.3 and 13.0 microns. Moderate resolution spectra of NGC 7027, HD 44179, BD+30 deg 3639, and IRAS 21282+5050 are presented which show evidence for new emission features centered near 12.0 and 12.7 microns. These are consistent with an origin from PAHs and can be used to constrain the molecular structure of the family of PAHs responsible for the infrared features. There is an indication that coronene-like PAHs contribute far more to the emission from NGC 7027 than to the emission from HD 44179. The observed asymmetric profile of the 11.3 micron band in all the spectra is consistent with the slight anharmonicity expected in the C-H out-of-plane bending mode in PAHs. A series of repeating features between 10 and 11 microns in the spectrum of HD 44179 suggests a simple hydride larger than 2 atoms is present in the gas phase in this object.

Witteborn, Fred C.↗

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

PAHs are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites, are identified, with a net abundance of about 0.0001 g/g (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins.

Sagan, Carl↗

Theoretical modeling of the infrared fluorescence from interstellar polycyclic aromatic hydrocarbons

We have modeled the family of interstellar IR emission bands at 3.3, 6.2, 7.7, 8.6, 11.3, and 12.7 microns by calculating the fluorescence from a size distribution of interstellar polycyclic aromatic hydrocarbons (PAHs) embedded in the radiation field of a hot star. It is found that the various emission bands are dominated by distinctly different PAHs, from molecules with much less than about 80 C atoms for the 3.3 micron feature, to molecules with 10 exp 2-10 exp 5 C atoms for the emission in the IRAS 12 and 25 micron bands. We quantitatively describe the influence on the emergent spectrum of various PAH properties such as the molecular structure, the amount of dehydrogenation, the intrinsic strength of the IR active modes, and the size distribution. Comparing our model results to the emission spectrum from the Orion Bar region, we conclude that interstellar PAHs are likely fully, or almost fully, hydrogenated. Moreover, it is found that the intrinsic strengths of the 6.2 and 7.7 micron C-C stretching modes, and the 8.6 micron C-H in-plane bending mode are 2-6 times larger than measured for neutral PAHs in the laboratory.

Schutte, W. A.↗

Benzenoid hydrocarbons in space: The evidence and implications

Many different celestial objects emit an infrared spectrum which has been attributed to infrared fluorescence from a family of highly vibrationally excited benzenoid hydrocarbons referred to as polycyclic aromatic hydrocarbons (PAHs). The most intense emitters contain between 20 to 50 carbon atoms, although larger species also contribute to the emission. This assignment is based on a rough resemblance of the interstellar emission spectra to the vibrational spectra of PAHs and related materials such as chars and soots which contain PAH mixtures. The spectroscopic assignments of the features between 3200 and 700/cm are discussed in detail. Much laboratory work on PAHs which are larger than those previously studied, isolated, ionized and dehydrogenated is called for to fully exploit this model. As PAHs are thought to be ubiquitous throughout the interstellar medium and more abundant than all other known polyatomic, interstellar molecules, they possess great potential as important probes of conditions in many different kinds of astronomical objects. Conversely, astronomical observations are extending our knowledge of these exotic materials by probing regions in which some conditions may be impossible to duplicate in the laboratory.

Allamandola, Louis J.↗

Evolution of macromolecular dust: Far-ultraviolet spectral dust extinction and gas absorption of stellar light as measured with the Hopkins Ultraviolet Telescope

From far-ultraviolet (FUV) spectra of B stars taken with the Hopkins Ultraviolet Telescope (HUT) and Voyager space observations, we determine the far-ultraviolet extinction by Galactic dust and hydrogen absorption in the local spiral-arm clouds towards HD 25443 (B0.5 III), HD 37903 (B1.5 V), and HD 200775 (B3 Ve). We find that the (n (H)) = 1.3 cu cm and number fraction (f = 0.31) of H atoms in molecular hydrogen relative to the total hydrogen indicates a mostly diffuse medium toward HD 25443. We also determine f = 0.56 for the gas in the photodissociation region (PDR) in front of HD 37903 and f approximately equals 0.36 for the HD 200775 PDR. The inferred ratios of N(H2)/I(CO) = 2.4 to 2.8 x 10(exp 20)/K(km/s)/sq cm for cool gas in dark clouds agree with previous canonical estimates of N(H2)/I(CO) = 2 to 3 x 10(exp 20)/K(km/s)/sq cm and support the use of the ratio for determining masses of molecular clouds. We find that the shape and strength of the HD 25443 FUV extinction is the same as a diffuse-medium mean extinction (R(sub nu) = 2.95) extrapolated from mid-UV wavelengths (normal). The HD 37903 FUV extinction through a bright H2 photodissociation region is higher than a mean FUV extinction(R(sub nu) = 4.11), as is the HD 200775 extinction. Another star from the literature rho Oph, probes the dense medium and exhibits an FUV extinction of normal mean strength (R(sub nu) = 4.55) but steeper shape. The normal FUV -extinction of HD 25443 implies that the small FUV-extinction dust in the diffuse medium forms in p art from larger grains as the grains shatter under shocks. The normal strength of the rho Oph FUV-extinction indicates that the minute dust condenses onto or coagulates into larger grains in the dense medium. The high extinction deviation of the HD 37903 PDR (and HD 200775 PDR) shows that FUV radiation from hot stars with T(sub eff) approximately equals 20,000 to 23,000 K in PDRs can evaporate some of the FUV-extinction dust from grain surfaces. In contrast, previously measured extinctions in Galactic H(+) (H II) regions shows that FUV radiation at T(sub eff) greater than 25,000 K can destroy some of the dust in H(+) regions. Thus, some of the FUV-extinction dust is highly volatile. We find that the dust carrier of the variable FUV-extinction is correlated (r = 0.99) with the mid-IR (12 micrometers) radiation from hydrocarbon dust. The volatile FUV-extinction component could thus be due to minute hydrocarbon dust particles or macromolecules, probably PAHs, which are known to condense onto larger grains in the dense medium. Larger grains compsed of PAHs clustered into a solid could thus produce the steep FUV extinction of the rho Oph dense medium. After exposure to FUV photons wihtin approximately 1 pc of HD 37903, PAHs with about 30 carbon atoms would evaporate off the larger grains, increasing gaseous PAH abundance by approximately 14%. Also, after receiving shocks in the diffuse medium toward HD 25443, the larger hydrocarbon grains would shatter into PAH molecules. In summary, as the Galactic medium cycles betwee n the diffuse and dense medium, hydrocarbon dust cycles into and out of larger grains under the influence of shocks, radiation, and condensation.

Buss, Richard H., Jr.↗

Chemical and Isotopic Analysis of Trace Organic Matter on Meteorites and Interstellar Dust Using a Laser Microprobe Instrument

Polycyclic Aromatic Hydrocarbons (PAHs) are of considerable interest today because they are ubiquitous on Earth and in the interstellar medium (ISM). In fact, about 20% of cosmic carbon in the galaxy is estimated to be in the form of PAHs. Investigation of these species has obvious uses for determining the cosmochemistry of the solar system. Work in this laboratory has focused on four main areas: 1) Mapping the spatial distribution of PAHs in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. 2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe Laser Desorption Ionization Mass Spectroscopy and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. 3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. 4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames. All areas involve elucidation of the solar system formation and chemistry using microprobe Laser Desorption Laser Ionization Mass Spectrometry. A brief description of microprobe Laser Desorption Ionization Mass Spectroscopy, which allows selective investigation of subattomole levels of organic species on the surface of a sample at 10-40 micrometer spatial resolution, is given.

Zare, Richard N.↗

Sublimation: A Mechanism for the Enrichment of Organics in Antarctic Ice

Recent analyses of the carbonate globules present in the Martian meteorite ALH84001 have detected polycyclic aromatic hydrocarbons (PAHs) at the ppm level. The distribution of PAHs observed in ALH84001 was interpreted as being inconsistent with a terrestrial origin and were claimed to be indigenous to the meteorite, perhaps derived from an ancient Martian biota. However, Becker et al., have examined PAHs in the Martian meteorite EETA79001, in several Antarctic carbonaceous chondrites and Antarctic Allan Hills Ice and detected many of the same PAHs found in ALH84001. The reported presence of L-amino acids of apparent terrestrial origin in the EETA79001 druse material, suggests that this meteorite is contaminated with terrestrial/extraterrestrial organics probably derived from Antarctic ice meltwater that had percolated through the meteorite. The detection of PAHs and L-amino acids in these Martian meteorites suggests that despite storage in the Antarctic ice, selective changes of certain chemical and mineralogical phases has occurred.

Becker, Luann↗

The Unidentified Infrared Emission Bands: Identified

The so-called Unidentified Infrared or simply UIR bands, the infrared emission band spectrum associated with a wide variety of interstellar objects, can be modeled in detail by laboratory spectra of neutral and positively charged polycyclic aromatic hydrocarbon (PAH) mixtures. Fits are presented for the UIR emission from the protoplanetary nebula IRAS 22272+5435, the diffuse galactic medium, and the Orion HII/photodissociation front - a selection of objects which span the evolutionary range of interstellar material. These data directly address the spectroscopic criticisms previously leveled at the PAH hypothesis and demonstrate that PAH-related molecular species are indeed responsible for this widespread emission. Furthermore, these fits reflect the structure, abundance, and ionization state of the interstellar PAHs and, in turn, provide direct insight into the processes of carbon nucleation, growth and evolution in circumstellar shells and the interstellar medium. To date, no other candidate material which has been proposed to account for the UIR emission can as readily and specifically reproduce these spectral variations. Given the ubiquity of these species, this work demonstrates the tremendous potential of these species as probes of a new and heretofore largely unexplored facet of astrochemistry - potential which should make PAHs the probe of the next millennium much as CO has been for the last quarter century.

Hudgins, Douglas M.↗

High Abundance of Ions in Cosmic Ices

Water-rich, mixed molecular ices and polycyclic aromatic hydrocarbons (PAHs) are common throughout interstellar molecular clouds and the Solar System. Vacuum ultraviolet (VUV) irradiation and particle bombardment of these abiotic ices produces complex organic species, including important biogenic molecules such as amino acids and functionalized PAHs which may have played a role in the origin of life. This ability of such water-rich, oxygen dominated ices to promote production of complex organic species is surprising and points to an important, unusual, but previously overlooked mechanism at play within the ice. Here we report the nature of this mechanism using electronic spectroscopy. VUV-irradiation of PAH/H2O ices leads to an unprecedented and efficient (greater than 70 %) conversion of the neutral PAHs to their cation form (PAH+). Further, these H2O/PAH+ ices are stabile at temperatures below 50 K, a temperature domain common throughout interstellar clouds and the Solar System. Between 50 and 125 K they react to form the complex organics. In view of this, we conclude that charged PAHs and other molecular ions should be common and abundant in many cosmic ices. The chemical, spectroscopic and physical properties of these ion-rich ices can be of fundamental importance for objects as diverse as comets, planets, and molecular clouds and may account for several poorly understood phenomena associated with each of these object classes.

Gudipati, Murthy S.↗

Evidence that Polycyclic Aromatic Hydrocarbons in Two Carbonaceous Chondrites Predate Parent-Body Formation

Organic material in meteorites provides insight into the cosmochemistry of the early solar system. The distribution of polycyclic aromatic hydrocarbons (PAHs) in the Allende and Murchison carbonaceous chondrites was investigated using spatially resolved microprobe laser-desorption laser-ionization mass spectrometry. Sharp chemical gradients of PAHs are associated with specific meteorite features. The ratios of various PAH intensities relative to the smallest PAH, naphthalene, are nearly constant across the sample. These findings suggest a common origin for PAHs dating prior to or contemporary with the formation of the parent body, consistent with proposed interstellar formation mechanisms.

Plows, F. L.↗

Infrared emission spectra of candidate interstellar aromatic molecules

Interstellar dust is responsible, through surface reactions, for the creation of molecular hydrogen, the main component of the interstellar clouds in which new stars form. Intermediate between small, gas-phase molecules and dust are the polycyclic aromatic hydrocarbons (PAHs). Such molecules could account for 2-30% of the carbon in the Galaxy, and may provide nucleation sites for the formation of carbonaceous dust. Although PAHs have been proposed as the sources of the unidentified infrared emission bands that are observed in the spectra of a variety of interstellar sources, the emission characteristics of such molecules are still poorly understood. Here we report laboratory emission spectra of several representative PAHs, obtained in conditions approximating those of the interstellar medium, and measured over the entire spectral region spanned by the unidentified infrared bands. We find that neutral PAHs of small and moderate size can at best make only a minor contribution to these emission bands. Cations of these molecules, as well as much larger PAHs and their cations, remain viable candidates for the sources of these bands.

Non-NASA Center↗

Polycyclic Aromatic Hydrocarbons and Infrared Astrophysics with Spitzer

PAH spectral features are now being used as new probes of the ISM. PAH ionization states reflect the ionization balance of the medium while PAH size and structure reflect the energetic and chemical history of the medium. This paper will focus on recent applications of the NASA Ames PAH IR spectral Database to interpret astronomical observations made by the Spitzer Space telescope and other space based infrared instruments. Examples will be given showing how changes in the spectral characteristics of different objects reveal interstellar PAH characteristics such as structure, size and composition, as well as provide insight into the chemical history and physical nature of the emission zones.

Allamandola, L. J.↗

Computational Spectroscopy of Polycyclic Aromatic Hydrocarbons In Support of Laboratory Astrophysics

Polycyclic aromatic hydrocarbons (PAHs) are strong candidates for the molecular carriers of the unidentified infrared bands (UIR) and the diffuse interstellar bands (DIBs). In order to test the PAH hypothesis, we have systematically measured the vibronic spectra of a number of jet-cooled neutral and ionized PAHs in the near ultraviolet (UV) to visible spectral ranges using the cavity ring-down spectroscopy. To support this experimental effort, we have carried out theoretical studies of the spectra obtained in our measurements. Ab initio and (time-dependent) density.functiona1 theory calculations are performed to obtain the geometries, energetics, vibrational frequencies, transition dipole moments, and normal coordinates of these PAH molecules. Franck-Condon (FC) calculations and/or vibronic calculations are then performed using the calculated normal coordinates and vibrational frequencies to simulate the vibronic spectra. It is found that vibronic interactions in these conjugated pi electron systems are often strong enough to cause significant deviations from the Born-Oppenheimer (BO) approximation. For vibronic transitions that are well described by the BO approximation, the vibronic band profiles are simulated by calculating the rotational structure of the vibronic transitions. Vibronic oscillator strength factors are calculated in the frame of the FC approximation from the electronic transition dipole moments and the FC factors. This computational effort together with our experimental measurements provides, for the first time, powerful tools for comparison with space-based data and, hence, a powerful approach to understand the spectroscopy of interstellar PAH analogs and the nature of the UIR and DIBs.

Tan, Xiaofeng↗

Investigations of the Formation of Carbon Grains in Circumstellar Outflows

The study of formation and destruction processes of cosmic dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. 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 carbonaceous dust. PAHs are important chemical building blocks of interstellar dust. They are detected in interplanetary dust particles and in meteoritic samples. Additionally, observational, laboratory, and theoretical studies have shown that PAHs, in their neutral and ionized forms, are an important, ubiquitous component of the interstellar medium. Also, the formation of PAHs from smaller molecules has not been extensively studied. Therefore, it is imperative that laboratory experiments be conducted to study the dynamic processes of carbon grain formation from PAH precursors. Studies of interstellar dust analogs formed from a variety of PAH and hydrocarbon precursors as well as species that include the atoms O, N, and S, have recently been performed in our laboratory under conditions that simulate interstellar and circumstellar environments. The species formed in the pulsed discharge nozzle (PDN) plasma source are detected and characterized with a high-sensitivity cavity ringdown spectrometer (CRDS) coupled to a Reflectron time-of-flight mass spectrometer (ReTOF-MS), thus providing both spectroscopic and ion mass information in-situ. We report the first set of measurements obtained in these experiments and identify the species present in the experiments and the ions that are formed in the plasma process. From these unique measurements, we derive information on the size and the structure of interstellar dust grain particles, the growth and the destruction processes of interstellar dust and the resulting budget of extraterrestrial organic molecules.

Grains↗

Hydrogen ejection from hydrocarbons: Characterization and relevance in soot formation and interstellar chemistry

Polycyclic aromatic hydrocarbons (PAHs) play a major role in the chemistry of combustion, pyrolysis, and the interstellar medium. Production (or activation) of radical PAHs and propagation of their resulting reactions require efficient dehydrogenation, but the preferred method of hydrogen loss is not well understood. Unimolecular hydrogen ejection (i.e., direct C─H bond fission) and bimolecular radical abstraction are two main candidate pathways. We performed a computational study to characterize the role of H ejection, particularly as a driver for radical-centric hydrocarbon-growth mechanisms and particle formation. Electronic structure calculations establish that C─H bond strengths span a broad range of energies, which can be weaker than 30 kcal/mol in some C 9 and C 13 PAH radicals. At T > 1200 K, calculated thermal rates for hydrogen ejection from weak C─H bonds at zigzag sites on PAH radicals are significantly larger than typical H-abstraction rates. These results are highly relevant in the context of chain reactions of radical species and soot inception under fuel-rich combustion conditions. Furthermore, calculated microcanonical rates that include the additional internal energy released by bond formation (e.g., ring closure to yield C 9 H 9 ) yield significantly higher rates than those associated with full thermalization. These microcanonical considerations are relevant to the astrochemical processes associated with hydrocarbon growth and processing in the low-density interstellar environment.

08 HYDROGEN↗

Aryl hydrocarbon receptor-dependent toxicity by retene requires metabolic competence

Polycyclic aromatic hydrocarbons (PAHs) are a class of organic compounds frequently detected in the environment with widely varying toxicities. Many PAHs activate the aryl hydrocarbon receptor (AHR), inducing the expression of a battery of genes, including xenobiotic metabolizing enzymes like cytochrome P450s (CYPs); however, not all PAHs act via this mechanism. We screened several parent and substituted PAHs in in vitro AHR activation assays to classify their unique activity. Retene (1-methyl-7-isopropylphenanthrene) displays Ahr2-dependent teratogenicity in zebrafish, but did not activate human AHR or zebrafish Ahr2, suggesting a retene metabolite activates Ahr2 in zebrafish to induce developmental toxicity. To investigate the role of metabolism in retene toxicity, studies were performed to determine the functional role of cyp1a, cyp1b1, and the microbiome in retene toxicity, identify the zebrafish window of susceptibility, and measure retene uptake, loss, and metabolite formation in vivo. Cyp1a-null fish were generated using CRISPR-Cas9. Cyp1a-null fish showed increased sensitivity to retene toxicity, whereas Cyp1b1-null fish were less susceptible, and microbiome elimination had no significant effect. Zebrafish required exposure to retene between 24 and 48 hours post fertilization (hpf) to exhibit toxicity. After static exposure, retene concentrations in zebrafish embryos increased until 24 hpf, peaked between 24 and 36 hpf, and decreased rapidly thereafter. We detected retene metabolites at 36 and 48 hpf, indicating metabolic onset preceding toxicity. This study highlights the value of combining molecular and systems biology approaches with mechanistic and predictive toxicology to interrogate the role of biotransformation in AHR-dependent toxicity.

59 BASIC BIOLOGICAL SCIENCES↗