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296 records · Page 17

Complex Organic Materials on Planetary Satellites and Other Small Bodies of the Solar System

The search for organic materials on small bodies of the Solar System is conducted spectroscopically from Earth-based telescopes and from spacecraft. Although the carbonaceous meteorites carry a significant inventory of complex organic solids, the sources of these meteorites have not been identified. Infrared spectra of a sample of the suspected sources, the C- and D-class asteroids, including new data from the Spitzer Space Telescope, show signatures of silicates, but none diagnostic of organic compounds. In the absence of discrete spectral features, the low albedos and colors in the visible and near-IR spectral regions are the principal links between the organic-bearing meteorites and the asteroids. While Pluto and a few trans-neptunian objects show spectral signatures of frozen CH4. Solid CH3OH has been identified on two Centaur objects in the outer Solar System. In some cases the red colors of those objects suggest the presence of tholins. The VIMS instrument aboard the Cassini spacecraft in orbit around Saturn has detected near-IR spectral features on at least three of Saturn's satellites that are indicative or suggestive of organic molecules. One entire hemisphere of the satellite Iapetus is covered with low-albedo material that shows a spectral signature of aromatic hydrocarbons (3.3 microns) and the -CH2 stretching mode bands of an aliphatic component. Organics absorbing at 3.44 microns are suspected in the region of the south pole of Enceladus, and also on the surface of Phoebe. Organic material may originate on icy bodies in the current epoch by various processes of energy deposition into native material, or they may fall to the surface from an external (probably cometary) source. Some organic material may be pre-solar, having originated in the interstellar medium before the formation of the Solar System. Using the techniques of remote sensing, its detection and analysis are slow and difficult.

Cruikshank, Dale P.↗

Low-Temperature Formation of Carbonaceous Grains from PAHs

Astronomical observations have detected interstellar carbon in the form of polycyclic aromatic hydrocarbons(PAHs) as well as carbonaceous dust, confirming its presence in both gaseous and solid phases. The goal of this study is to experimentally investigate low-temperature chemical pathways between these two phases in order to better understand the evolution of cosmic carbon. Cosmic dust analogs are produced in the supersonic expansion of an argon jet seeded with aromatic molecules: benzene, naphthalene, anthracene, phenanthrene, and pyrene. These are prototype aromatic molecules of compact and non compact structure, and are used to evaluate the effect of precursor structure on the molecular complexity of the resulting grains. The seeded jet is exposed to an electrical discharge and the carbonaceous grains are collected and probed ex situ via laser desorption mass spectrometry. Mass spectra reveal a rich molecular diversity within the grains, including fragments of the parent molecule but also growth into larger complex organic molecules (COMs). In all experiments, the largest number of products is found in the m/z range 200-250, and C16H10 (attributed to pyrene and/or its isomers) is found to be a dominant product, pointing at the formation of this stable PAH as a preferential route in the growth to larger PAHs. Comparison to mass spectra from the Murchison meteorite reveals a similar dominance of compounds related toC16H10 at m/z = 202. Evidence of the methyl addition-cyclization mechanism in the anthracene experiment is reported. PAH structure is found to impact the dust production yield, as seen by the greater yield for the anthracene compared to the phenanthrene experiment. PAH growth at low temperatures via barrierless routes involving the addition of alkyl- and phenyl-type radicals is suggested as a viable pathway to COMs. These results suggest that PAH growth and dust formation from PAHs are feasible at low temperatures in photon-dominated regions and circumstellar envelopes.

L Gavilan↗

New Anti-Corrosive Coatings with Resin-Bonded Polyaniline and Related Electroactive Groups

It is already known that polyaniline (an electroactive polymer) functions as a corrosion inhibitor for steel and in view of the fact that it is known to perform in the presence of hydrochloric acid, it has been considered likely that it may be useful to NASA for protecting launch structures at KSC which are exposed to not only continual ocean-side salt spray but also to hydrochloric acid at the times that solid-fuel boosters are fired. The currently used zinc-rich silicate-bonded coating is not wholly protective against the hydrochloric acid. Water pollution from zinc salts is another concern. Other earlier and concurrent NASA sponsored projects have been focussed on polyaniline specifically. Our project, administered for NASA by Dr. K. Thompson of KSC and these more-specifically polyaniline-related projects are included in a CRADA coordinated by Dr. F. Via of Akzo Nobel. A parallel project at Polytechnic under Prof K. Levon concentrated more specifically on polyaniline with various dopants. Our exploratory project reported herein was aimed at broadening the range of such corrosion inhibitors, to give protective paint compounders a wider latitude for adding corrosion inhibitors having polyaniline-like performance, and thus we diverged in several probing directions from polyaniline. Our working hypothesis was that physical variants of polyaniline, such as supported formulations on pigments or carriers, and chemical variants of polyaniline, including those having no electroconductive character, may have enhanced anticorrosion activity. We also hypothesized that small (non-polymeric) molecules having structures related to those occurring in polyaniline, may be active as corrosion inhibitors. We did preliminary testing, using an ASTM salt spray method at a nearby commercial paint testing laboratory. Our most interesting findings were that a non-electroconductive meta-isomer of polyaniline showed some corrosion activity, suggesting that the features of the polyaniline molecule associated with conductivity are not necessary for the anticorrosion action. Also, signtficantly, small molecular weight aromatic diamines and diimines resembling the reduced and the oxidized repeating unit in polyaniline showed an interesting degree of anticorrosive activity, suggesting that the polymeric feature of polyaniline is not necessary for anticorrosion action.

Weil, Edward D.↗

The Laboratory Production of Complex Organic Molecules in Simulated Interstellar Ices

Much of the volatiles in interstellar dense clouds exist in ices surrounding dust grains. Their low temperatures preclude most chemical reactions, but ionizing radiation can drive reactions that produce a suite of new species, many of which are complex organics. The Astrochemistry Lab at NASA-Ames studies the UV radiation processing of interstellar ice analogs to better identify the resulting products and establish links between interstellar chemistry, the organics in meteorites, and the origin of life on Earth. Once identified, the spectral properties of the products can be quantified to assist with the search for these species in space. Of particular interest are findings that UV irradiation of interstellar ice analogs produces molecules of importance in current living organisms, including quiriones, amphiphiles, and amino acids. Quinones play a variety of roles including electron transport and are used by all organisms. Studies show that quinones should be made wherever polycyclic aromatic hydrocarbons are irradiated in interstellar ices (Bernstein et al. 2001). Amphiphiles are also made when mixed molecular ices are irradiated. These amphiphiles self-assemble into membrane-walled vesicles when put in liquid water (Dworkin et al. 2001). Ice irradiation can also produce (Bernstein et al. 2002) and destroy amino acids (Ehrenfreund et al. 2001). Many of the same processes thought to make organics in space should yield products highly enriched in deuterium (D) (Sandford et al. 2001). The high D/H ratios in some interstellar species, and the knowledge that many of the organics in primitive meteorites are D-enriched, suggests that such linkages do exist. By using D as a tracer, we expect to learn more about the different chemical processes occurring in space and their relative importance in the production of different organic compounds and delivery to planetary surfaces.

Dworkin, Jason P.↗

Diversity in C-Xanes Spectra Obtained from Carbonaceous Solid Inclusions from Monahans Halite

Monahans meteorite (H5) contains fluid inclusion- bearing halite (NaCl) crystals [1]. Microthermometry and Raman spectroscopy showed that the fluid in the inclusions is an aqueous brine and they were trapped near 25degC [1]. Their continued presence in the halite grains requires that their incorporation into the H chondrite asteroid was post metamorphism [2]. Abundant solid inclusions are also present in the halites. The solid inclusions include abundant and widely variable organics [2]. Analyses by Raman microprobe, SEM/EDX, synchrotron X-ray diffraction and TEM reveal that these grains include macromolecular carbon similar in structure to CV3 chondrite matrix carbon, aliphatic carbon compounds, olivine (Fo99−59), high- and low-Ca pyroxene, feldspars, magnetite, sulfides, lepidocrocite, carbonates, diamond, apatite and possibly the zeolite phillipsite [3]. Here we report organic analyses of these carbonaceous residues in Monahans halite using C-, N-, and O- X-ray absorption near edge structure (XANES). Samples and Methods: Approximately 100 nm-thick sections were extracted with a focused ion beam (FIB) at JSC from solid inclusions from Monahans halite. The sections were analyzed using the scanning transmission X-ray microscope (STXM) on beamline 5.3.2.2 at the Advanced Light Source, Lawrence Berkeley National Laboratory for XANES spectroscopy. Results and Discussion: C-XANES spectra of the solid inclusions show micrometer-scale heterogeneity, indicating that the macromolecular carbon in the inclusions have complex chemical variations. C-XANES features include 284.7 eV assigned to aromatic C=C, 288.4-288.8 eV assigned to carboxyl, and 290.6 eV assigned to carbonate. The carbonyl features obtained by CXANES might have been caused by the FIB used in sample preparation. No specific N-XANES features are observed. The CXANES spectra obtained from several areas in the FIB sections include type 1&2 chondritic IOM like, type 3 chondritic IOM like, and none of the above. The natures of the macromolecular carbon in the solid inclusions observed by C-XANES are consistent with the previous studies showing that the carbonaceous solid inclusions have not originated from Monahans parent body [1-3], and have various origins, including various chondritic meteorite parent bodies as well as other unknown source(s).

Kebukawa, Y.↗

The Non-Destructive Separation of Diverse Astrobiologically Relevant Organic Molecules By Customizable Capillary Zone Electrophoresis and Monolithic Capillary Electrochromatography

The in situ detection of organic molecules in space is key to understanding the variety and the distribution of the building blocks of life, and possibly the detection of extraterrestrial life itself. Gas chromatography mass spectrometry (GC-MS) has been the most sensitive analytical instrument for organic analyses in flight, and was used on missions from NASA’s Viking, Phoenix, Curiosity missions to ESA’s Rosetta space probe. While pyrolysis GC-MS revealed the first organics on Mars, this step alters or degrades certain fragile molecules that are excellent biosignatures including polypeptides, oligonucleotides and polysaccharides, rendering the intact precursors undetectable. We have identified a solution tailored to the detection of biopolymers and other biomarkers by the use of liquid-based capillary electrophoresis and electrochromatography. In this study, we show that a capillary electrochromatography (CEC) approach using monolithic stationary phases with tailor-made surface chemistry can separate and identify various polycyclic aromatic hydrocarbons (PAHs), nucleobases and aromatic acids that could be formed under astrophysically relevant conditions. In order to simulate flyby organic sample capture, we conducted hypervelocity impact experiments which consisted of accelerating peptide-soaked montmorillonite particles to a speed of 5.6 km/sec, and capturing them in an amorphous silica aerogel of 10 and 30 mg/cc bulk density. Bulk peptide extraction from aerogel followed by capillary zone electrophoresis led to the detection of only two stereoisomeric peptide peaks. The recovery rates of each step of the extraction procedure after the hypervelocity impact suggest that major peptide loss occurred during the impact. Our study provides initial exploration of feasibility of this approach for capturing intact peptides, and subsequently detecting candidate biomolecules during flight missions that would be missed by GC-MS alone. As the monolith-based electrochromatography technology could be customized to detect specific classes of compounds as well as miniaturized, these results demonstrate the potential of the instrumentation for future astrobiology-related spaceflight missions.

Flyby sample return↗

Fluorescence Spectroscopy of Gas-phase Polycyclic Aromatic Hydrocarbons

The purpose of this investigation was to produce fluorescence spectra of polycyclic aromatic hydrocarbon (PAH) molecules in the gas-phase for comparison with blue luminescence (BL) emission observed in astrophysical sources Vijh et al. (2004, 2005a,b). The BL occurs roughly from 350 to 450 nm, with a sharp peak near 380 nm. PAHs with three to four rings, e.g. anthracene and pyrene, were found to produce luminescence in the appropriate spectral region, based on existing studies. Relatively few studies of the gas-phase fluorescence of PAHs exist; those that do exist have dealt primarily with the same samples commonly available for purchase such as pyrene and anthracene. In an attempt to understand the chemistry of the nebular environment we also obtained several nitrogen substituted PAHs from our colleagues at NASA Ames. In order to simulate the astrophysical environment we also took spectra by heating the PAHs in a flame. The flame environment counteracts the formation of eximers and permits the spectroscopy of free-flying neutral molecules. Experiments with coal tar demonstrate that fluorescence spectroscopy reveals primarily the presence of the smallest molecules, which are most abundant and which possess the highest fluorescence efficiencies. One gas-phase PAH that seems to fit the BL spectrum most closely is phenanthridine. In view of the results from the spectroscopy of coal tar, a compound containing a mixture of PAHs ranging from small to very large PAH molecules, we can not preclude the presence of larger PAHs in interstellar sources exhibiting BL.

Thomas, J. D.↗

Cavity Ring Down Spectroscopy of Cold Neutral Phenanthrene and Phenanthridine in Supersonic Jets

Here we study the effect of nitrogen insertion on the electronic spectra of polycyclic aromatic hydrocarbon (PAH) molecules measured under laboratory conditions that are relevant for comparison with astronomical data. We examine the case of the substitution of carbon atoms by nitrogen atoms in the benzenoid skeleton of phenanthrene (C 14 H 10 ), a prototype non-compact PAH. The vibronic transitions of the 2 1 A 1 (S 1 )←X 1 A 1 (S 0 ) electronic absorption band system of neutral phenanthrene (C 14 H 10 ) and phenanthridine (C 13 H 9 N) molecules seeded in a supersonic free jet expansion of argon gas are measured in the 315-345 nm region using the cavity ring down spectroscopy (CRDS) technique. Additional measurements of the absorption spectra of the phenanthrene, phenanthridine, and 1,10-phenanthroline (C 12 H 8 N 2 ) molecules isolated in 10-K solid argon matrices are also presented. The results obtained confirm that laboratory spectra of cold, isolated molecules obtained under astrophysically relevant conditions are required for a direct, unambiguous comparison with astronomical observations as well as for the understanding of the physical evolution of the interstellar medium.

Absorption band↗