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At least 397 records · Page 22

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NASA NTRS1995

Amino acid racemization on Mars: implications for the preservation of biomolecules from an extinct martian biota

Using kinetic data, we have estimated the racemization half-lives and times for total racemization of amino acids under conditions relevant to the surface of Mars. Amino acids from an extinct martian biota maintained in a dry, cold (<250 K) environment would not have racemized significantly over the lifetime of the planet. Racemization would have taken place in environments where liquid water was present even for time periods of only a few million years following biotic extinction. The best preservation of both amino acid homochirality and nucleic acid genetic information associated with extinct martian life would be in the polar regions.

NASA Discipline Exobiology↗

NASA NTRS1994

Isotopic analyses of nitrogenous compounds from the Murchison meteorite: ammonia, amines, amino acids, and polar hydrocarbons

The combined volatile bases (ammonia, aliphatic amines, and possibly other bases), ammonia, amino acids, and polar hydrocarbons were prepared from the Murchison meteorite for isotopic analyses. The volatile bases were obtained by cryogenic transfer after acid-hydrolysis of a hot-water extract and analyzed by combined gas chromatography-mass spectrometry of pentafluoropropionyl derivatives. The aliphatic amines present in this preparation comprise a mixture that includes both primary and secondary isomers through C5 at a total concentration of > or = 100 nmoles g-1. As commonly observed for meteoritic organic compounds, almost all isomers through C5 are present, and the concentrations within homologous series decrease with increasing chain length. Ammonia was chromatographically separated from the other volatile bases and found at a concentration of 1.1-1.3 micromoles g-1 meteorite. The ammonia analyzed includes contributions from ammonium salts and the hydrolysis of extractable organic compounds, e.g., carboxamides. Stable isotope analyses showed the volatile bases to be substantially enriched in the heavier isotopes, relative to comparable terrestrial compounds delta D < or = +1221%; delta 13C = +22%; delta 15N = +93%). Ammonia, per se, was found to have a somewhat lower delta 15N value (+69%) than the total volatile bases; consequently, a higher delta 15N (>93%) can be inferred for the other bases, which include the amines. Solvent-extractable polar hydrocarbons obtained separately were found to be enriched in 15N (delta 15N = +104%). Total amino acids, prepared from a hydrolyzed hot-water extract by cation exchange chromatography, gave a delta 15N of +94%, a value in good agreement with that obtained previously. Nitrogen isotopic data are also given for amino acid fractions separated chromatographically. The delta 15N values of the Murchison soluble organic compounds analyzed to date fall within a rather narrow range (delta 15N = +94 +/- 8%), an observation consistent with their formation, or formation of their precursors, by interstellar chemistry.

Non-NASA Center↗

NASA NTRS1986

Effects of norflurazon, an inhibitor of carotenogenesis, on abscisic acid and xanthoxin in the caps of gravistimulated maize roots

Maize seeds were germinated in the dark in the presence of the carotenoid synthesis inhibitor norflurazon and the levels of abscisic acid, xanthoxin and total carotenoids were measured in the root cap and in the adjacent 1.5 mm segment. In norflurazon-treated roots abscisic acid levels were markedly reduced, but an increase occurred in the levels of xanthoxin, a compound structurally and physiologically similar to abscisic acid. In the cultivar of maize (Zea mays L. cv. Merit) used for this work, brief illumination of the root is required for gravitropic curving. Following illumination both control and norflurazon-treated roots showed normal gravitropic curvature; however, the rate of curvature was delayed in norflurazon-treated roots. Our data from norflurazon-treated roots are consistent with a role for xanthoxin in maize root gravitropism. The increase in xanthoxin in the presence of an inhibitor of carotenoid synthesis suggests that xanthoxin and abscisic acid originate, at least in part, via different metabolic pathways.

NASA Program Space Biology↗

NASA NTRS1992

Novel long-chain anteiso-alkanes and anteiso-alkanoic acids in Antarctic rocks colonized by living and fossil cryptoendolithic microorganisms

Saponified extracts of rock samples colonized by cryptoendolithic microbial communities from the McMurdo Dry Valleys of Southern Victoria Land, Antarctica, were separated into hydrocarbon and fatty acid fractions by silica gel column chromatography. Hydrocarbons and methyl esters of fatty acids were analyzed by capillary gas chromatography-mass spectrometry. Unusually, a suite of long-chain anteiso-alkanes (a-C20 to a-C30) and anteiso-alkanoic acids (a-C20 to a-C30) were detected in many samples, together with straight-chain, branched and/or cyclic and acyclic isoprenoid compounds. These novel compounds are probably derived from unidentified heterotrophic bacteria or symbiotic processes in a unique microbial community in the Antarctic cold desert and suggest the occurrence of a special biosynthetic pathway. Long-chain anteiso-alkanes are probably formed through microbial decarboxylation of corresponding anteiso-alkanoic acids. They may serve as new biomarkers in environmental and geochemical studies.

NASA Program Exobiology↗

NASA NTRS1985

Infrared spectroscopic studies of the effect of elevated temperature on the association of pyroglutamic acid with clay and other minerals

Fourier transform i.r. measurements of L-pyroglutamic acid dispersed in a matrix of a clay, silica or alumina have been obtained at various temperatures between 25 and 220 degrees C. The i.r. spectrum of L-pyroglutamic acid varies in a manner dependent upon the matrix material and shows considerable change as the temperature of the mixtures is increased. The differences in the spectrum at elevated temperatures are explained in terms of a chemical reaction between hydroxyl groups in the matrix and the carboxylic acid. The i.r. spectra of trimethylsilyl derivatives of L-pyroglutamic acid and aluminum pyroglutamate were also measured to assist the understanding of spectra and interpretation of the spectral changes dependent upon increasing temperature.

Aluminum Oxide/analysis/chemistry↗

NASA NTRS2001

Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality

The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO(3)), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

Calcium Carbonate/metabolism↗

NASA NTRS1998

Polymerization on the rocks: beta-amino acids and arginine

We have studied the accumulation of long oligomers of beta-amino acids on the surface of minerals using the 'polymerization on the rocks' protocol. We find that long oligopeptides of beta-glutamic acid which cannot be formed in homogeneous aqueous solution are accumulated efficiently on the surface of hydroxylapatite using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDAC) as condensing agent. The EDAC-induced oligomerization of aspartic acid on hydroxylapatite proceeds even more efficiently. Hydroxylapatite can also facilitate the ligation of the tripeptide (glu)3. The 'polymerization on the rocks' scenario is not restricted to negatively-charged amino acids. Oligoarginines are accumulated on the surface of illite using carbonyldiimidizole (CDI) as condensing agent. We find that FeS2 catalyzes the CDI-induced oligomerization of arginine, although it does not adsorb oligoarginines. These results are relevant to the formation of polypeptides on the primitive earth.

NASA Discipline Exobiology↗

NASA NTRS1992

Permeability of lipid bilayers to amino acids and phosphate

Permeability coefficients for amino acid classes, including neutral, polar, hydrophobic, and charged species, were measured and compared with values for other ionic solutes such as phosphate. The rates of efflux of glycine, lysine, phenylalanine, serine and tryptophan were determined after they were passively entrapped in large unilamellar vesicles (LUVs) composed of egg phosphatidylcholine (EPC) or dimyristoylphosphatidylcholine (DMPC). The following permeability coefficients were obtained for: glycine, 5.7 x 10(-12) cm s-1 (EPC), 2.0 x 10(-11) cm s-1 (DMPC); serine, 5.5 x 10(-12) cm s-1 (EPC), 1.6 x 10(-11) cm s-1 (DMPC); lysine, 5.1 x 10(-12) cm s-1 (EPC), 1.9 x 10(-11) cm s-1 (DMPC); tryptophan, 4.1 x 10(-10) cm s-1 (EPC); and phenylalanine, 2.5 x 10(-10) cm s-1 (EPC). Decreasing lipid chain length increased permeability slightly, while variations in pH had only minor effects on the permeability coefficients of the amino acids tested. Phosphate permeability was in the range of 10(-12)-10(-13) cm s-1 depending on the pH of the medium. The values for the polar and charged amino acids were surprisingly similar to those previously measured for monovalent cations such as sodium and potassium, which are in the range of 10(-12)-10(-13) cm s-1, depending on conditions and the lipid species used. This observation suggests that the permeation rates for the neutral, polar and charged amino acids are controlled by bilayer fluctuations and transient defects, rather than partition coefficients and Born energy barriers. The results are relevant to the permeation of certain peptides into lipid bilayers during protein translocation and membrane biogenesis.

NASA Discipline Exobiology↗

NASA NTRS2005

Review of HxPyOz-Catalyzed H + OH Recombination in Scramjet Nozzle Expansions; and Possible Phosphoric Acid Enhancement of Scramjet Flameholding, from Extinction of H3PO4 + H2 - Air Counterflow Diffusion Flames

Recent detailed articles by Twarowski indicate that small quantities of phosphorus oxides and acids in the fuel-rich combustion products of H2 + phosphine (PH3) + air should significantly catalyze H, OH and O recombination kinetics during high-speed nozzle expansions -- to reform H2O, release heat, and approach equilibrium more rapidly and closely than uncatalyzed kinetics. This paper is an initial feasibility study to determine (a) if addition of phosphoric acid vapor (H3PO4) to a H2 fuel jet -- which is much safer than using PH3 -- will allow combustion in a high-speed scramjet engine test without adverse effects on localized flameholding, and (b) if phosphorus-containing exhaust emissions are environmentally acceptable. A well-characterized axisymmetric straight-tube opposed jet burner (OJB) tool is used to evaluate H3PO4 addition effects on the air velocity extinction limit (flame strength) of a H2 versus air counterflow diffusion flame. Addition of nitric oxide (NO), also believed to promote catalytic H-atom recombination, was evaluated for comparison. Two to five mass percent H3PO4 in the H2 jet increased flame strength 4.2%, whereas airside addition decreased it 1%. Adding 5% NO to the H2 caused a 2% decrease. Products of H-atom attack on H3PO4 produced an intense green chemiluminescence near the stagnation point. The resultant exothermic production of phosphorus oxides and acids, with accelerated H-atom recombination, released sufficient heat near the stagnation point to increase flame strength. In conclusion, the addition of H3PO4 vapor (or more reactive P sources) to hydrogen in scramjet engine tests may positively affect flameholding stability in the combustor and thrust production during supersonic expansion -- a possible dual benefit with system design / performance implications. Finally, a preliminary assessment of possible environmental effects indicates that scramjet exhaust emissions should consist of phosphoric acid aerosol, with gradual conversion to phosphate aerosol. This is compared to various natural abundances and sources.

Pellett, Gerald↗

NASA NTRS2005

Ice photochemistry as a source of amino acids and other organic molecules in meteorites, and implications for the origin of life and the search for life in the Solar System

The tons of extraterrestrial organic material that come to the Earth every day probably helped to made the Earth habitable, and possibly played a role in the origin of life. At the astrochemistry lab (http://www.astrochem.orq) we investigate the formation and distribution of organic molecules in space and consider the impact such molecules may have on the habitability of planets and the search for life in the Solar System. The organic compounds in meteorites include amino acids, aromatics of various sorts including purine and pyrimidine bases, and fatty acids that form bi-layer vesicles. The origin of many of these species remains mysterious, but in recent years we and others have performed experiments that suggest low temperature radiation chemistry could account for the presence and deuterium enrichment of many of these molecules. . I will present our laboratory experiments that show the viability of low temperature radiation chemistry as a source of organic molecules such as;amino acids (Nature, 2002, 416, 401-403), amphiphiles (Astrobiology, 2003, 2, 371, Proc. Nat. Acad. Sci. 2001, 98, 815), quinones (Science, 1999, 283, 1135) and other functionalized aromatic compounds (Meteoritics, 2001, 36, 351 ; Astrophysical Journal., 2003, 582, L25), some of which were invoked as potential biomarkers in the Alan Hills 84001 Martian meteorite. Understanding how components of proteins and DNA could form in sterile space environments is also of relevance to our search for life elsewhere in the Solar System, the great task now ahead of NASA. If we find evidence of Life elsewhere in the Solar System it will probably be in form of chemical biomarkers, quintessentially biological molecules that indicate the presence of micro-organisms. While most people think of molecules such as amino acids, and nucleo-bases as good candidate biomarkers, these molecules are produced non-biotically in space and are expected to be present on the surface of other planets even in the absence of Life. Understanding the range of non-biological organic molecules which could act as false biomarkers in space is a prerequisite for any reasonable search for Life on other worlds.

Bernstein, Max↗

NASA NTRS1980

Ambient cure polyimide foams prepared from aromatic polyisocyanates, aromatic polycarboxylic compounds, furfuryl alcohol, and a strong inorganic acid

Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, e.g., pyromellitic dianhydride, with an aromatic polyisocyanate, e.g., polymethylene polyphenylisocyanate (PAPI) in the presence of an inorganic acid and a lower molecular weight alcohol, e.g., dilute sulfuric acid or phosphoric acid and furfuryl alcohol. The exothermic reaction between the acid and the alcohol provides the heat necessary for the other reactants to polymerize without the application of any external heat. Such mixtures, therefore, are ideally suited for in situ foam formation, especially where the application of heat is not practical or possible.

Sawko, Paul M.↗

NASA NTRS2006

Acid Sulfate Weathering on Mars: Results from the Mars Exploration Rover Mission

Sulfur has played a major role in the formation and alteration of outcrops, rocks, and soils at the Mars Exploration Rover landing sites on Meridiani Planum and in Gusev crater. Jarosite, hematite, and evaporite sulfates (e.g., Mg and Ca sulfates) occur along with siliciclastic sediments in outcrops at Meridiani Planum. The occurrence of jarosite is a strong indicator for an acid sulfate weathering environment at Meridiani Planum. Some outcrops and rocks in the Columbia Hills in Gusev crater appear to be extensively altered as suggested by their relative softness as compared to crater floor basalts, high Fe(3+)/FeT, iron mineralogy dominated by nanophase Fe(3+) oxides, hematite and/or goethite, corundum-normative mineralogies, and the presence of Mg- and Casulfates. One scenario for aqueous alteration of these rocks and outcrops is that vapors and/or fluids rich in SO2 (volcanic source) and water interacted with rocks that were basaltic in bulk composition. Ferric-, Mg-, and Ca-sulfates, phosphates, and amorphous Si occur in several high albedo soils disturbed by the rover's wheels in the Columbia Hills. The mineralogy of these materials suggests the movement of liquid water within the host material and the subsequent evaporation of solutions rich in Fe, Mg, Ca, S, P, and Si. The presence of ferric sulfates suggests that these phases precipitated from highly oxidized, low-pH solutions. Several hypotheses that invoke acid sulfate weathering environments have been suggested for the aqueous formation of sulfate-bearing phases on the surface of Mars including (1) the oxidative weathering of ultramafic igneous rocks containing sulfides; (2) sulfuric acid weathering of basaltic materials by solutions enriched by volcanic gases (e.g., SO2); and (3) acid fog (i.e., vapors rich in H2SO4) weathering of basaltic or basaltic-derived materials.

Ming, Douglas W.↗

NASA NTRS2008

Compound-Specific Isotope Analysis of Amino Acids for Stardust-Returned Samples

Significant portions of the early Earth's prebiotic organic inventory , including amino acids, could have been delivered to the Earth's sur face by comets and their fragments. Analysis of comets via spectrosc opic observations has identified many organic molecules, including me thane, ethane, arnmonia, cyanic acid, formaldehyde, formamide, acetal ehyde, acetonitrile, and methanol. Reactions between these identifie d molecules could allow the formation of more complex organics such a s amino acids. Isotopic analysis could reveal whether an extraterrest rial signature is present in the Stardust-exposed amines and amino ac ids. Although bulk isotopic analysis would be dominated by the EACA contaminant's terrestrial signature, compoundspecific isotope analysi s (CSIA) could determine the signature of each of the other individua l amines. Here, we report on progress made towards CSIA of the amino acids glycine and EACA in Stardustreturned samples.

Cook, Jamie↗

NASA NTRS2010

Titanium Mass-balance Analysis of Paso Robles Soils: Elemental Gains and Losses as Affected by Acid Alteration Fluids

The Columbia Hills soils have been exposed to aqueous alteration in alkaline [1] as well as acid conditions [2,3]. The Paso Robles class soils are bright soils that possess the highest S concentration of any soil measured on Mars [2]. Ferric-sulfate detection by Moessbauer analysis indicated that acid solutions were involved in forming these soils [4]. These soils are proposed to have formed by alteration of nearby rock by volcanic hydrothermal or fumarolic activity. The Paso Robles soils consist of the original Paso Robles-disturbed-Pasadena (PR-dist), Paso Robles- PasoLight (PR-PL), Arad-Samra, Arad-Hula, Tyrone- Berker Island1 and Tyrone-MountDarwin [2 ,3. ]Chemical characteristics indicate that the PR-dist and PR-PL soils could be derived from acid weathering of local Wishstone rocks while the Samra and Hula soils are likely derived from local Algonquin-Iroquet rock [3]. The Paso Robles soils were exposed to acidic sulfur bearing fluids; however, little else is known about the chemistry of the alteration fluid and its effects on the alteration of the proposed parent materials. The objectives of this work are to conduct titanium normalized mass-balance analysis to1) assess elemental gains and losses from the parent materials in the formation of the Paso Robles soils and 2) utilize this information to indicate the chemical nature of the alteration fluids.

Sutter, Brad↗

NASA NTRS2010

Fungal Peptaibiotics: Assessing Potential Meteoritic Amino Acid Contamination

The presence of non-protein alpha-dialkyl-amino acids such as alpha-aminoisobutyric acid (alpha-A1B) and isovaline (Iva), which are relatively rare in the terrestrial biosphere, has long been used as an indication of the indigeneity of meteoritic amino acids, however, the discovery of alpha-AIB in peptides producers by a widespread group of filamentous fungi indicates the possibility of a terrestrial biotic source for the alpha-AIB observed in some meteorites. The alpha-AIB-containing peptides produced by these fungi are dubbed peptaibiotics. We measured the molecular distribution and stable carbon and nitrogen isotopic ratios for amino acids found in the total hydrolysates of four biologically synthesized peptaibiotics. We compared these aneasurenetts with those from the CM2 carbonaceous chondrite Murchison and from three Antarctic CR2 carbonaceous chondrites in order to understand the peptaibiotics as a potential source of meteoritic contamination.

Elsila, J. E.↗

NASA NTRS2003

Growth Conditions To Reduce Oxalic Acid Content of Spinach

A controlled-environment agricultural (CEA) technique to increase the nutritive value of spinach has been developed. This technique makes it possible to reduce the concentration of oxalic acid in spinach leaves. It is desirable to reduce the oxalic acid content because oxalic acid acts as an anti-nutritive calcium-binding component. More than 30 years ago, an enzyme (an oxidase) that breaks down oxalic acid into CO2 and H2O2 was discovered and found to be naturally present in spinach leaves. However, nitrate, which can also be present because of the use of common nitratebased fertilizers, inactivates the enzyme. In the CEA technique, one cuts off the supply of nitrate and keeps the spinach plants cool while providing sufficient oxygen. This technique provides the precise environment that enables the enzyme to naturally break down oxalate. The result of application of this technique is that the oxalate content is reduced by 2/3 in one week.

Johnson-Rutzke, Corinne↗

NASA NTRS2012

Comparing Amino Acid Abundances and Distributions Across Carbonaceous Chondrite Groups

Meteorites are grouped according to bulk properties such as chemical composition and mineralogy. These parameters can vary significantly among the different carbonaceous chondrite groups (CI, CM, CO, CR, CH, CB, CV and CK). We have determined the amino acid abundances of more than 30 primary amino acids in meteorites from each of the eight groups, revealing several interesting trends. There are noticeable differences in the structural diversity and overall abundances of amino acids between meteorites from the different chondrite groups. Because meteorites may have been an important source of amino acids to the prebiotic Earth and these organic compounds are essential for life as we know it, the observed variations of these molecules may have been important for the origins of life.

Burton, Aaron S.↗

NASA NTRS2012

Amino Acids and Chirality

Amino acids are among the most heavily studied organic compound class in carbonaceous chondrites. The abundance, distributions, enantiomeric compositions, and stable isotopic ratios of amino acids have been determined in carbonaceous chondrites fi'om a range of classes and petrographic types, with interesting correlations observed between these properties and the class and typc of the chondritcs. In particular, isomeric distributions appear to correlate with parent bodies (chondrite class). In addition, certain chiral amino acids are found in enantiomeric excess in some chondrites. The delivery of these enantiomeric excesses to the early Earth may have contributed to the origin of the homochirality that is central to life on Earth today. This talk will explore the amino acids in carbonaceous chondritcs and their relevance to the origin of life.

Cook, Jamie E.↗