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NASA NTRS1991

Self assembly properties of primitive organic compounds

A central event in the origin of life was the self-assembly of amphiphilic, lipid-like compounds into closed microenvironments. If a primitive macromolecular replicating system could be encapsulated within a vesicular membrane, the components of the system would share the same microenvironment, and the result would be a step toward true cellular function. The goal of our research has been to determine what amphiphilic molecules might plausibly have been available on the early Earth to participate in the formation of such boundary structures. To this end, we have investigated primitive organic mixtures present in carbonaceous meteorites such as the Murchison meteorite, which contains 1-2 percent of its mass in the form of organic carbon compounds. It is likely that such compounds contributed to the inventory of organic carbon on the prebiotic earth, and were available to participate in chemical evolution leading to the emergence of the first cellular life forms. We found that Murchison components extracted into non-polar solvent systems are surface active, a clear indication of amphiphilic character. One acidic fraction self-assembles into vesicular membranes that provide permeability barriers to polar solutes. Other evidence indicates that the membranes are bimolecular layers similar to those formed by contemporary membrane lipids. We conclude that bilayer membrane formation by primitive amphiphiles on the early Earth is feasible. However, only a minor fraction of acidic amphiphiles assembles into bilayers, and the resulting membranes require narrowly defined conditions of pH and ionic composition to be stable. It seems unlikely, therefore, that meteoritic infall was a direct source of membrane amphiphiles. Instead, the hydrocarbon components and their derivatives more probably would provide an organic stock available for chemical evolution. Our current research is directed at possible reactions which would generate substantial quantities of membranogenic amphiphiles. One possibility is photochemical oxidation of hydrocarbons.

Deamer, D. W.↗

NASA NTRS1992

Interstellar SiC with unusual isotopic compositions - Grains from a supernova?

Results are presented from an ion microprobe mass spectrometric analyses of five SiC grains from the Murchison carbonaceous meteorite. Unlike most interstellar SiC grains from primitive meteorites, the five grains from the Murchison meteorite show large excesses of C-12 (up to 28 times solar) and N-15 (up to 22 times solar), depletion in Si-29 and Si-30 (up to 59 percent), Al-26/Al-27 ratios between 0.1 and 0.6, and Ti-49 excesses up to 95 percent; in addition, one grain has a large Ca-44 excess (300 percent). The Ca and Ti anomalies point toward explosive nucleosynthesis in supernovae and the in situ decay of the radioactive precursors Ti-44 and V-49 in SiC grains formed in supernova ejecta. However, there is no simple formation scenario that can give a consistent explanation for the isotopic compositions of these grains.

Amari, Sachiko↗

NASA NTRS1989

Antarctic carbonaceous chondrites - New opportunities for research

An account is given of the types of carbonaceous meteorites available in the Antarctic collections of the U.S. and Japan. In the case of the collection for Victoria Land and Queen Maud Land, all known classes for meteorites except C1 are present; available pairing data, though limited, are indicative of the presence of many different falls. Thus far, attention has been focused on the largest meteorites. Most samples, however, are small.

Mcsween, Harry Y., Jr.↗

NASA NTRS1993

A reexamination of amino acids in lunar soil

Amino acids in lunar soils provide an important indicator of the level of prebiotic organic compounds on the moon. The results provide insight into the chemistry of amino acid precursors, and furthermore, given the flux of carbonaceous material to the moon, we can evaluate the survival of organics upon impact. The amino acid contents of both hydrolyzed and unhydrolyzed hot-water extracts of Apollo 17 lunar soil were determined using ophthaldialdehyde/N-acetyl cysteine (OPA/NAC) derivatization followed by HPLC analysis. Previous studies of lunar amino acids were inconclusive, as the technique used (derivatization with ninhydrin followed by HPLC analysis) was unable to discriminate between cosmogenic amino acids and terrestrial contaminants. Cosmogenic amino acids are racemic, and many of the amino acids found in carbonaceous meteorites such as Murchison, i.e., alpha-amino-i-butyric acid (aib), are extremely rare on Earth. The ninhydrin method does not distinguish amino acid enantiomers, nor does it detect alpha-alkyl amino acids such as aib, whereas the OPA/NAC technique does both.

Brinton, K. L. F.↗

NASA NTRS1993

Coagulation of grains in static and collapsing protostellar clouds

The wavelength dependence of extinction in the diffuse interstellar medium implies that it is produced by particles of dominant size of approximately 10(exp -5) cm. There is some indication that in the cores of dense molecular clouds, sub-micron grains can coagulate to form larger particles; this process is probably driven by turbulence. The most primitive meteorites (carbonaceous chondrites) are composed of particles with a bimodal size distribution with peaks near 1 micron (matrix) and 1 mm (chondrules). Models for chondrule formation that involve processing of presolar material by chemical reactions or through an accretion shock during infall assume that aggregates of the requisite mass could form before or during collapse. The effectiveness of coagulation during collapse has been disputed; it appears to depend on specific assumptions. The first results of detailed numerical modeling of spatial and temporal variations of particle sizes in presolar clouds, both static and collapsing, is reported in this article.

Weidenschilling, S. J.↗

NASA NTRS1996

The Composition of Planetesimal 5145 Pholus

We present a new spectrum of 5145 Pholus between 1.15 and 2.4 microns. We model this, and the previously published (0.4-1.0 microns) spectrum, using Hapke scattering theory. The 2.04 micron band of H2O ice is seen in absorption, as well as a strong band at 2.27 Am, interpreted as frozen methanol and/or the methanol photo product hexamethylenetetramine (HMT). The presence of small molecules is indicative of a chemically primitive surface, since heating removes the light hydrocarbons in favor of macromolecular carbon typically found in carbonaceous meteorites. The unusually red slope of Pholus' spectrum is matched by fine grains of Titan tholin, as found previously. Object 1993 HA2, which has an orbit similar to that of 5145 Pholus, is similarly red, but there are as yet no observations of absorption bands in its spectrum. We present a model for the composite spectrum of all spectroscopic and photometric data available for 5145 Pholus and conclude that this is a primitive object which has yet to be substantially processed by solar heat.

Cruikshank, D. P.↗

NASA NTRS1997

Observations and Modeling of the Transient General Circulation of the North Pacific Basin

The objective of this study was to clarify the role that interstellar-cloud chemistry played in forming the population of organic molecules presently found in carbonaceous meteorites. This goal was to be achieved by means of defining the isotopic components present in organic and related phases in the meteorites and thereby identify the processes and source reservoirs involved in organic synthesis in the early solar system. Isotopic analysis of separated amino acids from the Murchison meteorite yielded results that are complex and not fully interpretable at this time. Substantial inter-acid variability in D/H ratio was observed, some but not all of which could be attributed to exchange with terrestrial hydrogen. Pronounced, though smaller, variability was also found for N-15/N-14 ratios. For both D/H and N-15/N-14 data, observed meteoritic values were substantially greater than found in terrestrial materials, providing a robust constraint on degrees of possible terrestrial contamination. Also, C-13/C-12 ratios, though falling within the range of data found on earth, significantly exceeded those characteristic of naturally occurring terrestrial amino acids. Inter-acid variability in C-13/C-12 ratios was muted relative to that observed for D/H and N-15/N-14 but still lay well outside of experimental uncertainty. No systematic relationship could be observed between variations in H, C and N isotopes. Two anomalous components were also found during the course of this study. A highly (greater than 6% relative to terrestrial) N-15-depleted, N-rich compound, which has not yet been identified, co-eluted with some amino acids. Clearly the Murchison meteorite sampled nitrogen from a number of highly diverse isotopic reservoirs. In fact, from this and related studies, it is now apparent that the distribution of nitrogen isotopes in the primitive solar system was extremely inhomogeneous. The second anomalous result obtained in the present study was for an extract of 'ammonia' from Murchison. It should be noted that this sample consisted of ammonia that was probably derived from a number of different compounds present in the meteorite itself, possibly including amines and amides, as well as ammonia sensu strictu and ammonium slats. However, the significance of this analysis is that the N-15/N-14 ratio measured was much lower than those found for the meteoritic amino acids (+2% vs around + 9% relative to terrestrial). This raises an important question concerning the source of the ammonia that was involved in synthesis of the amino acids. This issue needs to be explored further.

Kerridge, John F.↗

NASA NTRS1997

Nucleosynthesis and the Isotopic Composition of Stardust

Various components have been isolated from carbonaceous meteorites with an isotopically anomalous elemental composition. Several of these are generally thought to represent stardust containing a nucleosynthetic record of their birthsites. This paper discusses the expected isotopic composition of stardust based upon astronomical observations and theoretical studies of their birthsites: red giants and supergiants, planetary nebulae, C-rich Wolf-Rayet stars, novae and supernovae. Analyzing the stardust budget, it is concluded that about 15% of the elements will be locked up in stardust components in the interstellar medium. This stardust will be isotopically heterogenous on an individual grain basis by factors ranging from 2 to several orders of magnitude. Since comets may have preserved a relatively unprocessed record of the stardust entering the solar nebula, isotopic studies of returned comet samples may provide valuable information on the nucleosynthetic processes taking place in the interiors of stars and the elemental evolution of the Milky Way.

Tielens, Alexander G. M.↗

NASA NTRS1999

Bacterial Paleontology and Studies of Carbonaceous Chondrites

The study of the fossilization processes of modern cyanobacteria provides insights needed to recognize bacterial microfossils. The fossilization of cyanobacteria is discussed and images of recent and fossil bacteria and cyanobacteria from the Early Proterozoic to Neogene carbonaceous rocks (kerites, shungites, and black shales) and phosphorites are provided. These are compared with biomorphic microstructures and possible microfossils encountered in-situ in carbonaceous meteorites.

Gerasimenko, L. M.↗

NASA NTRS1998

The Composition of Centaur 5145 Pholus

We present a new spectrum of the Centaur object 5145 Pholus between 1.15 and 2.4 micro meters. We model this, and the previously published (0.4- to 1.0- micrometer) spectrum, using Hapke scattering theory. Seen in absorption are the 2.04- micrometer band of H2O ice and a strong band at 2.27 micrometer, interpreted as frozen methanol and/or a photolytic product of methanol having small molecular weight. The presence of small molecules is indicative of a chemically primitive surface, since heating and other processes remove the light hydrocarbons in favor of macromolecular carbon of the kind found in carbonaceous meteorites. The unusually red slope of Pholus' spectrum is matched by fine grains of a refractory organic solid (tholin). Olivine (which we model with Fo 82) also appears to be present on Pholus. We present a five-component model for the composite spectrum of all spectroscopic and photometric data available for 5145 Pholus and conclude that this is a primitive object which has not yet been substantially processed by solar heat. The properties of Pholus are those of the nucleus of a large comet that has never been active.

Cruikshank, D. P.↗

NASA NTRS1996

Integrated Microchemical Analysis System Using DS2 Penetrator Technology for the Enantiomeric Detection of Amino Acids

Any strategy for investigating whether abiotic and/or biotic organic molecules are present on Mars and the search for biosignatures should focus on compounds which are readily synthesized under plausible prebiotic conditions, play an essential role in biochemistry as we know it and have properties such as chirality (handedness) which can be used to distinguish between abiotic vs. biotic origins (1). Amino acids are one of the few compound classes that fulfill all these requirements. They are synthesized in high yields in prebiotic simulation experiments, are one of the more abundant types of organic compounds present in carbonaceous meteorites and only the L-enantiomers are used in the proteins and enzymes in life on Earth.

Frank J Grunthaner↗

NASA NTRS1994

Light-Hydrocarbon Bearing Solids on Planetesimal 5145 Pholus

Object 5145 Pholus (=1992 AD) is a planetesimal in an orbit that crosses those of Saturn, Uranus, and Neptune (period 92.7 years). It is particularly notable because of its extreme red color, corroborated by several observing teams. A spectrum of Pholus obtained in 1992 shows a strong absorption band with a characteristic shape at 2.27 micrometers, plus a weaker band at 1.7 micrometers. A better spectrum of the 2.0-2.5 micrometer region in 1993 confirms the position and shape of the 2.27-micrometer band. The color and spectral bands are identified with the aliphatic-rich and high H/C organic solid called asphaltite, which in a terrestrial setting originates from thermal processing of products of biological activity. In Pholus, this material is attributed to formation from radiation processing of ices on grains in the interstellar medium. Laboratory spectra of asphaltite and related materials have been published by Moroz et al., while Cloutis showed similar bands in comparable materials and identified them as the overtone and combination bands of C-H stretching and bending modes in CH2 and CH3 groups. Asphaltites, kerites, and anthraxolites are solid non-graphite members of a sequence ranging from oil to graphite; diffuse reflectance spectra of suites of these intermediate materials show color characteristics similar to those of the low-albedo asteroids (C,P,D), although specific identifications have not been made because of the lack of distinct absorption bands in the spectra of most low-albedo solar system bodies. In the case of Pholus, however, the primary band is strong; its wavelength and its shape, plus the match of the extremely red color, leads us to the identification of aliphatic-rich, asphaltite-like organic solid. The C, P, and D-type asteroids vary in degree of "redness", but are all less red than Pholus. Pholus and the Ctype asteroids are the end members of a sequence that represents the radiation processing of hydrocarbons, with Pholus being the least processed. Solar irradiation processes and heating reduce the H/C and aliphatic content of hydrocarbons preserved from the interstellar medium, and in the end produce opaque solids of neutral reflectance, including the kerogens (similar to anthraxolites) found in profusion in the carbonaceous meteorites.

Cruikshank, Dale P.↗

NASA NTRS1994

Light-Hydrocarbon Bearing Solids on Planetesimal 5145 Pholus

Object 5145 Pholus (=1992 AD) is a planetesimal in an orbit that crosses those of Saturn, Uranus, and Neptune (period 92.7 years). It is particularly notable because of its extreme red color, corroborated by several observing teams. A spectrum of Pholus obtained in 1992 shows a strong absorption band with a characteristic shape at 2.27 micron, plus a weaker band at 1.7 microns. A better spectrum of the 2.0-2.5 micron region in 1993 confirms the position and shape of the 2.27 micron band. The color and spectral bands are identified with the aliphatic-rich and high H/C organic solid called asphaltite, which in a terrestrial setting originates from thermal processing of products of biological activity. In Pholus, this material is attributed to formation from radiation processing of ices on grains in the interstellar medium. Laboratory spectra of asphaltite and related materials have been published by Moroz et al., while Cloutis showed similar bands in comparable materials and identified them as the overtone and combination bands of C-H stretching and bending modes in CH2 and CH3 groups. Asphaltites, kerites, and anthraxolites are solid non-graphite members of a sequence ranging from oil to graphite; diffuse reflectance spectra of suites of these intermediate materials show color characteristics similar to those of the low-albedo asteroids (C,P,D), although specific identifications have not been made because of the lack of distinct absorption bands in the spectra of most low-albedo solar system bodies. In the case of Pholus, however, the primary band is strong; its wavelength and its shape, plus the match of the extremely red color, leads us to the identification of aliphatic-rich, asphaltite-like organic solid. The C, P, and D-type asteroids vary in degree of 'redness', but are all less red than Pholus. Pholus and the C-type asteroids are the end members of a sequence that represents the radiation processing of hydrocarbons, with Pholus being the least processed. Solar irradiation processes and heating reduce the H/C and aliphatic content of hydrocarbons preserved from the interstellar medium, and in the end produce opaque solids of neutral reflectance, including the kerogens (similar to anthraxolites) found in profusion in the carbonaceous meteorites.

Cruikshank, Dale P.↗

NASA NTRS2003

High-Resolution Electrospray Ionization/Ion Mobility Spectrometer for Detection of Abiotic Amino Acids

One of the primary goals of the current NASA thrust in Astrobiology is the detection and identification of organic molecules as part of an in-situ lander platform on the surface of Mars or Europa. The identification of these molecules should help determine whether indigenous organisms exist on the surface of Mars or in an undersea environment on Europa. In addition, a detailed organic chemical inventory of surface and near surface molecules will help elucidate the possibilities of life elsewhere in the Universe. Terrestrial life has, as its backbone, the family of molecules known as the amino acids (AA), and while AA can be found in the terrestrial environments as part of more complex molecules, such as peptides, and proteins, they also exist as individual molecules due to of the hydrolyses of biopolymers. In terrestrial biochemistry, there are 20 principal amino acids which are necessary for life. However, some forms of these molecules can be found in nature synthesized via abiotic process. For example, they are known to exist extraterrestrially as a component of carbonaceous meteorites. The idea that amino acids are readily created by abiotic means has been demonstrated by their positive identification in the Murchison CM2 meteorite, which fell in 1969. This meteorite was analyzed before contamination by terrestrial microbes could result. Three laboratories individually tested parts of the meteorite and concluded that the amino acids present in them were indigenous to the meteorite because, among other reasons, they had equal L- and D- enantiomers. Final identification of the constituents of the Murchison included 33 amino acids which have no known biotic source, 11 amino acids which have limited distribution and 8 (Glycine, Alanine, Valine, Proline, Leucine, Isoleucine, Aspartic Acid, and Glutamic Acid), which readily occur in terrestrial proteins.

L W Beegle↗

NASA NTRS2003

Framboidal Structures in Earth Rocks and in Astromaterials

Framboidal structures are common both in Earth rocks and in meteorites - carbonaceous chondrites. The main methods of formation of these structures are discussed. The role of biologic factors in formation of framboids is evaluated. Comparison of crystal forms comprising framboids formed in laboratory conditions and in nature is provided. On the basis of investigations of framboidal structures the proposition that pyritoidal form of crystals is typical for the formation of biogenic framboidal structures.

Astafieva, M. M.↗

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 NTRS2005

Electron Beam Analysis of Micrometeoroids Captured in Aerogel as Stardust Analogues

In January 2004, NASA s Stardust spacecraft passed through the tail of Comet 81P/Wild-2. The on-board dust flux monitor instrument indicated that numerous micro- and nano-meter sized cometary dust particles were captured by the dedicated silica aerogel capture cell. The collected cometary particles will be returned to Earth in January 2006. Current Stardust analogues are: (i) Light-gas-gun accelerated individual mineral grains and carbonaceous meteoritic material in aerogels at the Stardust encounter velocity ca.approximately 6 kilometers per second. (ii) Aerogels exposed in low-Earth orbit (LEO) containing preserved cosmic dust grains. Studies of these impacts offer insight into the potential state of the captured cometary dust by Stardust and the suitability of various analytical techniques. A number of papers have discussed the application of sophisticated synchrotron analytical techniques to analyze Stardust particles. Yet much of the understanding gained on the composition and mineralogy of interplanetary dust particles (IDPs) has come from electron microscopy studies. Here we discuss the application of scanning electron microscopy (SEM) for Stardust during the preliminary phase of post-return investigations.

Graham, G. A.↗

NASA NTRS2006

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.↗