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NASA NTRS2006

From Astrochemistry to Astrobiology ...... and Back Again

Tremendous strides have been made in our understanding of interstellar material over the past twenty five years thanks to significant developments in observational infrared astronomy and laboratory astrophysics. Twenty five years ago the composition of interstellar dust was largely guessed at, the concept of ices in dense molecular clouds generally ignored, and the notion of large, abundant, gas phase, carbon-rich molecules widespread throughout the interstellar medium (ISM) considered impossible. Today the composition of interstellar dust is reasonably well understood. In molecular clouds, the birthplace of stars and planets, these cold dust particles are coated with mixed molecular ices whose composition is reasonably 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 spectroscopic studies of interstellar space, combined with laboratory simulations and theoretical studies of PAHs and interstellar ices, have revealed the widespread presence of interstellar PAHs and the composition of interstellar precometary ices. The remainder of the presentation will focus on the photochemical evolution of these icy materials. Within a molecular cloud, and especially the presolar nebula, materials frozen into the ices are photoprocessed by ultraviolet light and more complex molecules are produced. As these materials are the building blocks of comets and related to carbonaceous micrometeorites, they are likely to be important sources of complex materials delivered to habitable planets and their composition may be related to the origin of life.

Allamandola, L. J.↗
NASA NTRS2006

Laboratory Spectroscopy of Large Carbon Molecules and Ions in Support of Space Missions

One of the major objectives of Laboratory Astrophysics is the optimization of data return from space missions by measuring spectra of atomic and molecular species in laboratory environments that mimic interstellar conditions (WhitePaper (2002, 2006)). Among interstellar species, PAHs are an important and ubiquitous component of carbon-bearing materials that represents a particularly difficult challenge for gas-phase laboratory studies. We present the absorption spectra of jet-cooled neutral and ionized PAHs and discuss the implications for astrophysics. The harsh physical conditions of the interstellar medium have been simulated in the laboratory. We are now, for the first time, in the position to directly compare laboratory spectra of PAHs and carbon nanoparticles with astronomical observations. This new phase offers tremendous opportunities for the data analysis of current and upcoming space missions geared toward the detection of large aromatic systems (HST/COS, FUSE, JWST, Spitzer).

Salana, Farid↗
NASA NTRS2007

Variations of the Mid-IR Aromatic Features Inside and Among Galaxies

We present the results of a systematic study of mid-IR spectra of Galactic regions, Magellanic H II regions, and galaxies of various types (dwarf, spiral, starburst), observed by the satellites ISO and Spitzer. We study the relative variations of the 6.2, 7.7, 8.6 and 11.3 micron features inside spatially resolved objects (such as M 82, M 51, 30 Doradus, M 17 and the Orion bar), as well as among 90 integrated spectra of 50 objects. Our main results are that the 6.2, 7.7 and 8.6 micron bands are essentially tied together, while the ratios between these bands and the 11.3 micron band varies by one order of magnitude. This implies that the properties of the PAHs are remarkably universal throughout our sample, and that the relative variations of the band ratios are mainly controlled by the fraction of ionized PAHs. In particular, we show that we can rule out the modification of the PAH size distribution as an explanation of these variations. Using a few well-studied Galactic regions (including the spectral image of the Orion bar), we give an empirical relation between the I(6.2)/I(11.3) ratio and the ionization/recombination ratio Go/n(sub e) x square root of(T(sub gas)). Finally, we discuss the physical interpretation of the I(6.2)/I(11.3) ratio, on galactic size scales.

Galliano, F.↗
NASA NTRS2009

Heavy Ion Formation in Titan's Ionosphere: Magnetospheric Introduction of Free Oxygen and a Source of Titan's Aerosols?

Discovery by Cassini's plasma instrument of heavy positive and negative ions within Titan's upper atmosphere and ionosphere has advanced our understanding of ion neutral chemistry within Titan's upper atmosphere, primarily composed of molecular nitrogen, with approx.2.5% methane. The external energy flux transforms Titan's upper atmosphere and ionosphere into a medium rich in complex hydrocarbons, nitriles and haze particles extending from the surface to 1200 km altitudes. The energy sources are solar UV, solar X-rays, Saturn's magnetospheric ions and electrons, solar wind and shocked magnetosheath ions and electrons, galactic cosmic rays (CCR) and the ablation of incident meteoritic dust from Enceladus' E-ring and interplanetary medium. Here it is proposed that the heavy atmospheric ions detected in situ by Cassini for heights >950 km, are the likely seed particles for aerosols detected by the Huygens probe for altitudes <100km. These seed particles may be in the form of polycyclic aromatic hydrocarbons (PAH) containing both carbon and hydrogen atoms CnHx. There could also be hollow shells of carbon atoms, such as C60, called fullerenes which contain no hydrogen. The fullerenes may compose a significant fraction of the seed particles with PAHs contributing the rest. As shown by Cassini, the upper atmosphere is bombarded by magnetospheric plasma composed of protons, H(2+) and water group ions. The latter provide keV oxygen, hydroxyl and water ions to Titan's upper atmosphere and can become trapped within the fullerene molecules and ions. Pickup keV N(2+), N(+) and CH(4+) can also be implanted inside of fullerenes. Attachment of oxygen ions to PAH molecules is uncertain, but following thermalization O(+) can interact with abundant CH4 contributing to the CO and CO2 observed in Titan's atmosphere. If an exogenic keV O(+) ion is implanted into the haze particles, it could become free oxygen within those aerosols that eventually fall onto Titan's surface. The process of freeing oxygen within aerosols could be driven by cosmic ray interactions with aerosols at all heights. This process could drive pre-biotic chemistry within the descending aerosols. Cosmic ray interactions with grains at the surface, including water frost depositing on grains from cryovolcanism, would further add to abundance of trapped free oxygen. Pre-biotic chemistry could arise within surface microcosms of the composite organic-ice grains, in part driven by free oxygen in the presence of organics and any heat sources, thereby raising the astrobiological potential for microscopic equivalents of Darwin's "warm ponds" on Titan.

Sittler, E. C., Jr.↗
NASA NTRS2012

Observations of Herbig Ae/Be Stars with Herschel/PACS: The Atomic and Molecular Contents of Their Protoplanetary Discs

We observed a sample of 20 representative Herbig Ae/Be stars and 5 A-type debris discs with PACS onboard Herschel, as part of the GAS in Protoplanetary Systems (GASPS) project. The observations were done in spectroscopic mode, and cover the far-infrared lines of [OI], [CII], CO, CH+, H20, and OH. We have a [OI]63 micro/ detection rate of 100% for the Herbig Ae/Be and 0% for the debris discs. The [OI] 145 micron line is only detected in 25% and CO J = 18-17 in 45% (and fewer cases for higher J transitions) of the Herbig Ae/Be stars, while for [CII] 157 micron, we often find spatially variable background contamination. We show the first detection of water in a Herbig Ae disc, HD 163296, which has a settled disc. Hydroxyl is detected as well in this disc. First seen in HD 100546, CH+ emission is now detected for the second time in a Herbig Ae star, HD 97048. We report fluxes for each line and use the observations as line diagnostics of the gas properties. Furthermore, we look for correlations between the strength of the emission lines and either the stellar or disc parameters, such as stellar luminosity, ultraviolet and X-ray flux. accretion rate, polycyclic aromatic hydrocarbon (PAH) band strength, and flaring. We find that the stellar ultraviolet flux is the dominant excitation mechanism of [OI] 63 micron, with the highest line fluxes being found in objects with a large amount of flaring and among the largest PAH strengths. Neither the amount of accretion nor the X-ray luminosity has an influence on the line strength. We find correlations between the line flux of [OI]63 micron and [OI] 145 micron, CO J = IS-17 and [OI] 6300 A, and between the continuum flux at 63 micron and at 1.3 mm, while we find weak correlations between the line flux. of [OI] 63 micron and the PAH luminosity, the line flux of CO J = 3-2, the continuum flux at 63 pm, the stellar effective temperature, and the Br-gamma luminosity. Finally, we use a combination of the [OI] 63 micron and C(12)O J = 2-1 line fluxes to obtain order of magnitude estimates of the disc gas masses, in agreement with the values that we find from detailed modelling of two Herbig Ae/Be stars, HD 163296 and HD 169142.

Meeus, G.↗
NASA NTRS2012

GASPS Observations of Herbig Ae/Be Stars with PACS/Herschel: The Atomic and Molecular Content of Their Protoplanetary Discs

We observed a sample of 20 representative Herbig Ae/Be stars and five A-type debris discs with PACS onboard of Herschel. The observations were done in spectroscopic mode, and cover far-IR lines of [O I], [C II], CO, CH+, H2O and OH. We have a [O I] 63 micron detection rate of 100% for the Herbig Ae/Be and 0% for the debris discs. [O I] 145 micron is only detected in 25 %, CO J=18-17 in 45 % (and less for higher J transitions) of the Herbig Ae/Be stars and for [C II] 157 micron, we often found spatially variable background contamination. We show the first detection of water in a Herbig Ae disc, HD 163296, which has a settled disc. Hydroxyl is detected as well in this disc. CH+, first seen in HD 100546, is now detected for the second time in a Herbig Ae star, HD 97048. We report fluxes for each line and use the observations as line diagnostics of the gas properties. Furthermore, we look for correlations between the strength of the emission lines and stellar or disc parameters, such as stellar luminosity, UV and X-ray flux, accretion rate, PAH band strength, and flaring. We find that the stellar UV flux is the dominant excitation mechanism of [O I] 63, with the highest line fluxes found in those objects with a large amount of flaring and greatest PAH strength. Neither the amount of accretion nor the X-ray luminosity has an influence on the line strength. We find correlations between the line flux of [O I] 63 and [O I] 145, CO J = 18-17 and [O I] 6300 A, and between the continuum flux at 63 micron and at 1.3 mm, while we find weak correlations between the line flux of [O I] 63 and the PAH luminosity, the line flux of CO J = 3-2, the continuum flux at 63 micron, the stellar effective temperature and the Br(gamma) luminosity. Finally, we use a combination of the [O I] 63 and CO-12 J = 2-1 line fluxes to obtain order of magnitude estimates of the disc gas masses, in agreement of the values we found from detailed modelling of 2 HAEBEs, HD 163296 and HD 169142.

G Meeus↗
NASA NTRS2012

Exploring the Connection Between Star Formation and AGN Activity in the Local Universe

We study a combined sample of 264 star-forming, 51 composite, and 73 active galaxies using optical spectra from SDSS and mid-infrared (mid-IR) spectra from the Spitzer Infrared Spectrograph. We examine optical and mid-IR spectroscopic diagnostics that probe the amount of star formation and relative energetic con- tributions from star formation and an active galactic nucleus (AGN). Overall we find good agreement between optical and mid-IR diagnostics. Misclassifications of galaxies based on the SDSS spectra are rare despite the presence of dust obscuration. The luminosity of the [NeII] 12.8 micron emission-line is well correlated with the star formation rate (SFR) measured from the SDSS spectra, and this holds for the star forming, composite, and AGN-dominated systems. AGN show a clear excess of [NeIII] 15.6 micron emission relative to star forming and composite systems. We find good qualitative agreement between various parameters that probe the relative contributions of the AGN and star formation, including: the mid-IR spectral slope, the ratio of the [NeV] 14.3 micron to [NeII] micron 12.8 fluxes, the equivalent widths of the 7.7, 11.3, and 17 micron PAH features, and the optical "D" parameter which measures the distance a source lies from the locus of star forming galaxies in the optical BPT emission-line diagnostic diagram. We also consider the behavior of the three individual PAH features by examining how their flux ratios depend upon the degree of AGN-dominance. We find that the PAH 11.3 micron feature is significantly suppressed in the most AGN-dominated systems.

LaMassa, Stephanie M.↗
NASA NTRS2013

New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.

Bugga, Ratnakumar V.↗
NASA NTRSDate not supplied

Computing rovibrational, vibrational, and cascade emission spectra for comparison to astronomical observations

Over the last several years, our group has been involved in developing approaches to compute highly accurate spectroscopic constants and vibrational frequencies for small transient molecules that may be used in the interpretation and assignment of high-resolution laboratory experiments as well as high-resolution astronomical spectra. Additionally, we have used the computed spectroscopic constants to simulate purely rotational and rovibrational spectra so that these may be compared directly with high-resolution astronomical observations, and we have worked on developing approaches that can be applied to much larger molecules, such as polycyclic aromatic hydrocarbon (PAH) molecules, where we can explicitly determine anharmonic corrections to vibrational frequencies as well as take into account intensity sharing due to resonances. In addition, for PAH molecules we have used the anharmonic data to compute a library of temperature-dependent anharmonic vibrational spectra, with proper inclusion of polyad resonances, which can then be used to model the cascade emission spectra of PAH molecules – the type of spectra directly observed by astronomers. Another part of our work in spectroscopic signatures involves computing highly accurate line lists for common molecules, such as CO2, SO2, and NH3, which occur in many astrophysical environments, including the atmospheres of exoplanents, and often need to have their lines identified in high-resolution observations in order to determine which lines are due to other molecules. In order to characterize the atmospheres of hot exoplanets, these line lists need to be very accurate and extend to very high energies. I will discuss our latest work in these areas of astrochemical spectroscopy research.

Timothy J Lee↗
NASA NTRSDate not supplied

ICEE: Next Generation Exobiology and Astrobiology Studies

The presence of organic molecules, from simple to complex form are found in the ISM (interstellar medium). Perhaps the largest of these molecules are the PAHs, or polycyclic aromatic hydrocarbons, while smaller versions of PAHs have been identified in meteorites, IDPs (interplanetary dust particles) and comets within the Solar System. Life is comprised of organic molecules and, in one sense; the search for life is the search for and identification of organic molecules. This yields an interesting question. Can the organics in the ISM serve as the chemical feedstock to the prebiotic molecules identified in meteorites, comets and IDPs in a “Top-Down” synthesis mechanism? Most studies regarding the formation of prebiotic molecules focus on a “Bottoms-Up” mechanism, whereby simple organic compounds in ice form larger, more biologically relevant molecules when exposed to UV irradiation. Here we present a next generation experimental setup which focuses on if larger, interstellar organics, such as PAHs (polycyclic aromatic hydrocarbons) can serve as the chemical feedstock for the organic inventory found in the Solar System.

A. L. Mattioda↗
DOE OSTI2020

Metal Bioavailability and Ecotoxicity of Bioremediated Oils and Tailings by BioTiger{sup TM}, a Microbial Consortium

Oil Sands and Mature Fine Tailings: Oil sand reserves are a major source of oil for the United States. Oil sands are a mixture of sand, clay, water, and bitumen. The refining process requires large volumes of water and generates hazardous Mature Fine Tailings (MFTs) that are stored in engineered settling ponds. They are of major environmental concern due to their persistence and difficulty to naturally biodegrade. MFT Contaminants of Concern: Naphthenic Acids (NAs), Polycyclic Aromatic Hydrocarbons (PAHs), Benzene, Toluene, Ethylbenzene and Xylene (BTEX), Metals, Residual Bitumen. BioTiger{sup TM} (BT{sup TM}), the SRNL patented 12 component microbial consortia was found to cometabolically degrade some NAs and PAHs. Previous studies performing short term exposure (48 hours and 7 days) to BT{sup TM} have resulted in increased toxicity due to the partial degradation of PAHs forming toxic intermediates. Objective: Evaluate the ecotoxicity of BT{sup TM} remediated MFTs exposed to a 2 week period w/ yeast (Y) extract. This work will determine BT{sup TM}'s remediation of MFTs from Fort McMurray, Alberta. Acute toxicity tests will be performed under section 9 of EPA's Method for Measuring Acute Toxicity using the freshwater organism, Ceriodaphnia dubia. Monitor BT{sup TM} growth through Most Probable Number (MPN) counts, pH, and metal bioavailability will also be evaluated. Preparing tailing solutions for biodegradation: BT{sup TM} components were grown in R2A media and combined. Mother BT{sup TM} was centrifuged at 7000 rpm for 20 minutes and resuspended in Bushnell Haus. 33 g of tailings were added to 1100 mL Bushnell Haus along with yeast extract (11 g) to create a 3% tailing solution. Treatments were performed in triplicate. Preparing solutions for toxicity tests using C. dubia: Supernatant was collected immediately after centrifuging at 7000 rpm for 20 min. Supernatant was filtered via a 0.22 μm sterile system. All treatments except MFT, Y peaked at T=4. This decrease in microbial growth could be associated with toxicity from intermediate byproducts. Treatments containing only MFTs decreased in the initial 11 days before growing significantly. Final solution for MFT, Y treatment had the highest pH. This could potentially be due to increased microbial activity linked with yeast consumption. All treatments except MFT, Y peaked at T=4. This decrease in microbial growth could be associated with toxicity from intermediate byproducts. Treatments containing only MFTs decreased in the initial 11 days before growing significantly. Future Direction: Await results from Acute Toxicity Tests and Metal Bioavailability Quantification of biosurfactant production. Evaluate hydrocarbon degradation byproducts using an analytical chemistry approach. More toxicity experiments with variations in time and conditions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Styrene Thermal Decomposition and Its Reaction with Acetylene under Shock Tube Pyrolysis Conditions: an Experimental and Kinetic Modeling Study

Styrene is an important compound for polymer production and a key intermediate in gas-phase kinetics of polycyclic aromatic hydrocarbons (PAHs). For the first time, the pyrolysis of styrene with and without the presence of acetylene is investigated in a single-pulse shock tube coupled to gas chromatography and mass spectrometry. For each reaction system, quantitative speciation profiles are probed within the temperature range of 1100-1730 K, nominal pressure of 20 bar, and reaction duration of similar to 4 ms. A kinetic model is built to simulate the results. The model explains how styrene is consumed under high-pressure pyrolytic conditions, how the secondary chemistry of intermediate products affect subsequent PAH formation, and how acetylene addition alters the reaction pathways. Throughout the temperature range, styrene breakdown is dominated by the bimolecular interaction between styrene and hydrogen atom, which produces benzene+vinyl or phenyl and ethylene through the stabilization of 2-phenylethyl and its subsequent dissociation. As a result, large amounts of phenyl accumulate, which react with styrene to form C14H12 species while simultaneously releasing H atoms through addition/elimination reactions. The reactivity of fuel consumption is preserved by the regeneration of H atoms as chain carriers. Several C14H10 compounds are formed as a result of the following breakdown of the C14H12 isomers, particularly stilbene, 1,1-diphenyl ethylene, and 9-methyl-9H-fluorene. The presence of acetylene as a co-reactant with styrene allows the Hydrogen-Abstraction-Acetylene-Addition (HACA) pathway to proceed from phenyl radical to enhance the production of phenylacetylene at very low temperatures and acenaphthylene. This hinders the formation of C14H12 isomers, exclusive products from pure styrene dissociation by competing with the styrene+phenyl routes.

Kinetic Modeling↗
DOE OSTI2020

Identification of the molecular-weight growth reaction network in counterflow flames of the C 3 H 4 isomers allene and propyne

The reaction networks responsible for aromatics formation in counterflow flames of the C 3 H 4 isomers allene and propyne are identified through a combined experimental and modeling study. Mole fraction profiles of near-atmospheric pressure (933 mbar) diffusion flames fueled by the C 3 H 4 isomers are analyzed by means of a newly assembled, chemically detailed kinetic mechanism. The experiment consists of a counterflow burner system that is coupled to a high-resolution time-of-flight molecular-beam mass spectrometer with single-photon ionization via synchrotron-generated vacuum-ultraviolet photons. Flame-sampled, mass-specific photoionization efficiency curves are used to identify the presence of aliphatically substituted aromatic species in addition to the commonly considered pericondensed ring structures. The new mechanism describes the formation and growth of aromatics through repetitive sequences of radical–radical and radical–molecule reactions that include C 1 6 intermediates. Higher concentrations of aromatic species are observed in the allene flame and the new mechanism captures the observed experimental trends very accurately. The results indicate the importance of the aliphatically substituted aromatics and of ring-enlargement reactions for the growth reactions. According to the model simulations, radical+radical recombination and PAH-radical+molecule reactions play an important role in PAH growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Formation of five-membered ring structures via reactions of o -benzyne

The formation of five-membered ring structures is important for the generation of curved and bowl-shaped polycyclic aromatic hydrocarbons (PAHs) under combustion conditions. Here, we report the identification of the indenyl (C 9 H 7 ) radical – the simplest aromatic hydrocarbon radical carrying an adjacent five- and six-membered ring, as the major product of the o-benzyne (o-C 6 H 4 ) reaction with propargyl (C 3 H 3 ). Because real flames exhibit a complex chemistry, elucidation of a specific reaction is very challenging. Instead, we studied the o-C 6 H 4 + C 3 H 3 reaction in a resistively heated microtubular SiC reactor at controlled conditions of 1150 K and a pressure near 10–20 Torr. To this end, the reactants o-benzyne and propargyl were pyrolytically generated from benzoyl chloride and propargyl bromide. We identified the reactants and the indenyl radical isomer-selectively utilizing photoion mass-selected threshold photoelectron spectroscopy (ms-TPES). In conclusion, the experimentally observed predominant formation of indenyl radicals finally confirms the theoretical predictions of Matsugi and Miyoshi [Phys. Chem. Chem. Phys. 14 (2012), 9722–9728] and highlights a versatile route for the formation of five-membered rings and curved PAHs via reactions of o-benzyne that favor the formation of multiring species over aliphatically substituted aromatic species.

Molecular-weight growth↗
DOE OSTI2021

Translating dosimetry of Dibenzo[ def,p ]chrysene (DBC) and metabolites across dose and species using physiologically based pharmacokinetic (PBPK) modeling

We report that Dibenzo[def,p]chrysene (DBC) is an environmental polycyclic aromatic hydrocarbon (PAH) that causes tumors in mice and has been classified as a probable human carcinogen by the International Agency for Research on Cancer. Animal toxicity studies often utilize higher doses than are found in relevant human exposures. Additionally, like many PAHs, DBC requires metabolic bioactivation to form the ultimate toxicant, and species differences in DBC and DBC metabolite metabolism have been observed. To understand the implications of dose and species differences, a physiologically based pharmacokinetic model (PBPK) for DBC and major metabolites was developed in mice and humans. Metabolism parameters used in the model were obtained from experimental in vitro metabolism assays using mice and human hepatic microsomes. PBPK model simulations were evaluated against mice dosed with 15 mg/kg DBC by oral gavage and human volunteers orally microdosed with 29 ng of DBC. DBC and its primary metabolite DBC-11,12-diol were measured in blood of mice and humans, while in urine, the majority of DBC metabolites were obeserved as conjugated DBC-11,12-diol, conjugated DBC tetrols, and unconjugated DBC tetrols. The PBPK model was able to predict the time course concentrations of DBC, DBC-11,12-diol, and other DBC metabolites in blood and urine of human volunteers and mice with reasonable accuracy. Agreement between model simulations and measured pharmacokinetic data in mice and human studies demonstrate the success and versatility of our model for interspecies extrapolation and applicability for different doses. Furthermore, our simulations show that internal dose metrics used for risk assessment do not necessarily scale allometrically, and that PBPK modeling provides a reliable approach to appropriately account for interspecies differences in metabolism and physiology.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Fragmentation Dynamics of Fluorene Explored Using Ultrafast XUV-Vis Pump-Probe Spectroscopy

We report on the use of extreme ultraviolet (XUV, 30.3 nm) radiation from the Free-electron LASer in Hamburg (FLASH) and visible (Vis, 405 nm) photons from an optical laser to investigate the relaxation and fragmentation dynamics of fluorene ions. The ultrashort laser pulses allow to resolve the molecular processes occurring on the femtosecond timescales. Fluorene is a prototypical small polycyclic aromatic hydrocarbon (PAH). Through their infrared emission signature, PAHs have been shown to be ubiquitous in the universe, and they are assumed to play an important role in the chemistry of the interstellar medium. Our experiments track the ionization and dissociative ionization products of fluorene through time-of-flight mass spectrometry and velocity-map imaging. Multiple processes involved in the formation of each of the fragment ions are disentangled through analysis of the ion images. The relaxation lifetimes of the excited fluorene monocation and dication obtained through the fragment formation channels are reported to be in the range of a few tens of femtoseconds to a few picoseconds.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Formation of phenanthrene via H–assisted isomerization of 2–ethynylbiphenyl produced in the reaction of phenyl with phenylacetylene

Model chemistry G3(MP2,CC)//B3LYP/6–311G(d,p) calculations of the potential energy surface for the reaction of phenyl radical (C 6 H 5 ) with phenylacetylene (C 8 H 6 ) have been carried out and combined with Rice–Ramsperger–Kassel–Marcus/Master Equation calculations of temperature– and pressure–dependent rate constants. The results showed that the reaction can serve as a viable source for the formation of phenanthrene via an indirect route involving a primary reaction of phenyl addition to the ortho carbon in the ring of phenylacetylene and H elimination producing 2–ethynylbiphenyl followed by secondary H–assisted isomerization of 2–ethynylbiphenyl to phenanthrene. In the secondary reaction, the H atom adds to the α carbon of the ethynyl side chain, then a six–member ring closure takes place followed by aromatization via an H loss. The channel of H addition to the side chain of 2–ethynylbiphenyl appears to be much faster than H addition to the ortho carbon in the ethynyl–substituted ring leading back to the initial C 6 H 5 + C 8 H 6 reactants. Rate constants for the primary C 6 H 5 + C 8 H 6 ⇌2–ethynylbiphenyl (p1) + H and secondary p1 + H⇌phenanthrene (p2) + H reactions have been computed in the temperature range of 500–2500 K at pressures of 30 Torr, 1, 10, and 100 atm and fitted to modified Arrhenius expressions. Here, the suggested kinetic scheme and rate constants are proposed as a prototype for the modeling of the growth of polycyclic aromatic hydrocarbons via the phenyl addition–dehydrocyclization (PAC) mechanism involving an addition of a PAH radical to an ethynyl–substituted PAH molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Planar, curved and twisted molecular nanographenes: Reduction-induced alkali metal coordination

Planar and curved polycyclic aromatic hydrocarbons (PAHs) attract significant attention as molecular models of fullerenes, carbon nanotubes, and graphene, thus stimulating broad investigation of chemical reactivity and materials applications of designed nanocarbon π-systems. Non-planar molecular nanographenes (NGs) recently emerge as advanced anode materials in energy storage, showing high reduction limits and enhanced alkali metal intercalation levels. However, the lack of direct structure–property correlations in such complex hybrid systems impedes their further development and utilization. With a focus on alkali-metal-induced reduction of selected PAHs, we herein review original metal binding and intercalation trends, site specific coordination, and distinct carbon framework responses to stepwise electron uptake. Small planar graphene fragments, like triphenylene and coronene, are compared to π-expanded hexabenzocoronenes, followed by the discussion of bowl-shaped corannulene, sumanene and other carbon bowls, as well as bent, warped, and twisted molecular nanographenes. The effect of size, symmetry, and framework topology along with the structural deformation of carbon backbones upon reduction are analyzed, using recent crystallographic examples of alkali-metal intercalated products. In conclusion, the revealed insights into the structures, binding, and metal intercalation in molecular nanographenes should stimulate their future applications as new functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗