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At least 127 records · Page 7

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NASA NTRS1975

Ultraviolet-gas phase and -photocatalytic synthesis from CO and NH3

Ammonium cyanate is identified as the major product of the photolysis of gaseous NH3-CO mixtures at 206.2 or 184.9 nm. Lesser amounts of urea, biurea, biuret semicarbazide, formamide and cyanide are observed. A series of 18 reactions underlying the formation of photolysis products is presented and discussed. Photocatalytic syntheses of C-14-urea, -formamide, and -formaldehyde are carried out through irradiation of (C-14)O and NH3 in the presence of Vycor, silica gel, or volcanic ash shale surfaces. The possible contributions of the relevant reactions to the abiotic synthesis of organic nitrogen compounds on Mars, the primitive earth, and in interstellar space are examined.

Hubbard, J. S.↗

NASA NTRS1975

Asymmetric adsorption by quartz - A model for the prebiotic origin of optical activity

One mechanism previously proposed for the abiotic accumulation of molecules of one chirality in nature is asymmetric adsorption on the chiral surfaces of optically active quartz crystals. Earlier literature in this field is reviewed, with the conclusion that previous investigations of this phenomenon, using optical rotation criteria, have afforded ambiguous results. We now have studied the adsorption of radioactive D- and L-alanine on powdered d- and l-quartz, using change in radioactivity level as a criterion for both gross and differential adsorption, d-Quartz preferentially adsorbed D-alanine from anhydrous dimethyl-formamide solution, and l-quartz L-alanine. The differential adsorption varied between 1.0 and 1.8%. The implications of these observations are discussed from the viewpoint of early chemical evolution and the origin of optically active organic compounds in nature.

Bonner, W. M.↗

NASA NTRS1975

Stereoisomers of isovaline in the Murchison meteorite

Isovaline is present in the Murchison meteorite as a racemic mixture (about equal concentrations of the R and S enantiomers). Since isovaline does not have a hydrogen atom on its asymmetric alpha-carbon atom, the racemic mixture could not have formed by commonly accepted mechanisms of racemization. Thus, isovaline in the meteorite most probably was synthesized as a racemic mixture and is not the result of the racemization of either the R or S enantiomer. Other chiral amino acids in the meteorite are present as racemic mixtures, and were probably synthesized in a similar manner by abiotic, extraterrestrial processes.

Pollock, G. E.↗

NASA NTRS1975

The optical nature of methylsuccinic acid in human urine

Methylsuccinic acid was isolated from human urine, derivatized as the di-S-(+)-2-butyl ester, and analyzed using a gas chromatographic system capable of separating the enantiomers of the derivative. The R-(+)-isomer was found to be present. Methylsuccinic acid is potentially important as a criterion for abiogenicity, having been obtained as a racemic mixture from sources known to be abiotic.

Zeitman, B.↗

NASA NTRS1976

Space exploration and the history of solar-system volatiles

The thermochemical history of volatile substances in all solar-system planets, satellites, and planetoids is discussed extensively. The volatiles are viewed as an interface between the abiotic and biotic worlds and as a key to the history of bodies of the solar system. A flowsheet of processes and states is exhibited. Differences in bulk volatiles distribution between the planetary bodies and between the interior, surface, and atmosphere of each body are considered, as well as sinks for volatiles in degassing. The volatiles-rich Jovian and Saturnian satellites, the effect of large-planet magnetosphere sweeps on nearby satellites, volatiles of asteroids and comets, and the crucial importance of seismic, gravity, and libration data are treated. A research program encompassing analysis of the elemental and isotopic composition of rare gas in atmospheres, assay of volatiles-containing phases in regoliths, and examination of present or past atmospheric escape/accretion processes is recommended.

Fanale, F. P.↗

NASA NTRS1976

Melanoidin and aldocyanoin microspheres - Implications for chemical evolution and early Precambrian micropaleontology

Two new classes of organic microspheres are described. One of them (melanoidin) is synthesized from amino acids and sugars in heated aqueous solutions. The other (aldocyanoin) is formed in aqueous solutions of ammonium cyanide and formaldehyde at room temperature. The general properties of these microspheres, including conditions of synthesis, size and shape, mechanical and pH stability, and solubility, are compared with corresponding properties of other protocell model systems. It is concluded that melanoidin and aldocyanoin microspheres are plausible candidates for precellular units in the primitive hydrosphere. Since the bulk of the organic carbon in early Precambrian sediments is insoluble kerogen-melanoidin, it is suggested that some Precambrian microfossils may be abiotic melanoidin microspheres.

Kenyon, D. H.↗

NASA NTRS1976

Are the oldest 'fossils', fossils

A comparative statistical study has been carried out on populations of modern algae, Precambrian algal microfossils, the 'organized elements' of the Orgueil carbonaceous meteorite, and the oldest microfossil-like objects now known (spheroidal bodies from the Fig Tree and Onverwacht Groups of the Swaziland Supergroup, South Africa). The distribution patterns exhibited by the more than 3000 m.y.-old Swaziland microstructures bear considerable resemblance to those of the abiotic 'organized elements' but differ rather markedly from those exhibited by younger, assuredly biogenic, populations. Based on these comparisons, it is concluded that the Swaziland spheroids could be, at least in part, of nonbiologic origin; these oldest known fossil-like microstructures should not be regarded as constituting firm evidence of Archean life.

Schopf, J. W.↗

NASA NTRS1980

A continuation of base-line studies for environmentally monitoring space transportation systems at John F. Kennedy Space Center. Executive summary

Studies conducted in and around John F. Kennedy Space Center, Merrit Island, Florida were designed to establish baseline conditions for various attributes of the biotic and abiotic environment. Features were described and quantitatively measured. Certain condition were found to be appropriate for the detection and assessment of possible environmental perturbations caused by future NASA activities. These include plant communities, mammal populations, rainfall chemistry, fish populations, and the status of rare and endangered species. On the basis of statistical analysis of quantitative data and logistic considerations, it was possible to refine the kinds and amounts of measurements needed to evaluate perturbations in selected environmental components.

Stout, I. J.↗

NASA NTRS1979

Amino acids in the Yamato carbonaceous chrondrite from Antarctica

Evidence for the presence of amino acids of extraterrestrial origin in the Antarctic Yamato carbonaceous chrondrite is presented. Hydrolyzed and nonhydrolyzed water-extracted amino acid samples from exterior, middle and interior portions of the meteorite were analyzed by an amino acid analyzer and by gas chromatography of N-TFA-isopropyl amino acid derivatives. Nine protein and six nonprotein amino acids were detected in the meteorite at abundances between 34 and less than one nmole/g, with equal amounts in interior and exterior portions. Nearly equal abundances of the D and L enantiomers of alanine, aspartic acid and glutamic acid were found, indicating the abiotic, therefore extraterrestrial, origin of the amino acids. The Antarctic environment and the uniformity of protein amino acid abundances are discussed as evidence against the racemization of terrestrially acquired amino acids, and similarities between Yamato amino acid compositions and the amino acid compositions of the Murchison and Murray type II carbonaceous chrondrites are indicated.

Shimoyama, A.↗

NASA NTRS1979

Quantification of monocarboxylic acids in the Murchison carbonaceous meteorite

The abundances of some of the straight- and branched-chain isomers of the monocarboxylic acids found in the Murchison carbonaceous chondrite are determined. Monocarboxylic acids extracted from a crushed sample of Murchison interior were quantified by means of gas chromatography and mass spectroscopy after a spiking solution of deuterated analogues of 11 carboxylic acids had been added. Monocarboxylic acid abundances are found to range between 1.83 and 0.01 micromole/g, which is significantly higher than Murchison amino acid concentrations, and to decrease with increasing carbon number for both branched and unbranched molecules. The results are interpreted to support the abiotic extraterrestrial synthesis of monocarboxylic acids. Possible mechanisms leading to the equal synthesis of branched and each unbranched carboxylic acid with the same carbon number are considered, noting that the Fischer-Tropsch Type mechanism by itself is incapable of accounting for the observed distributions.

Lawless, J. G.↗

NASA NTRS1980

Organic compounds in meteorites

Recent studies of carbonaceous chondrites provide evidence that certain organic compounds are indigenous and the result of an abiotic, chemical synthesis. The results of several investigators have established the presence of amino acids and precursors, mono- and dicarboxylic acids, N-heterocycles, and hydrocarbons as well as other compounds. For example, studies of the Murchison and Murray meteorites have revealed the presence of at least 40 amino acids with nearly equal abundances of D and L isomers. The population consists of both protein and nonprotein amino acids including a wide variety of linear, cyclic, and polyfunctional types. Results show a trend of decreasing concentration with increasing carbon number, with the most abundant being glycine (41 n Moles/g). These and other results to be reviewed provide persuasive support for the theory of chemical evolution and provide the only natural evidence for the protobiological subset of molecules from which life on earth may have arisen.

Lawless, J. G.↗

NASA NTRS1980

Experiments on the amplification of optical activity

Chemical mechanisms for the amplification of small, abiotically produced enantiomeric excesses leading to the complete stereo specificity of all biochemical reactions observed in the present-day biosphere are investigated quantitatively. Partial copolymerization of a mixture of R- and S-leucine or R- and S-valine N-carboxy anhydrides containing a known excess of one enantiomer was induced and the enantiomeric composition of the resulting oligomer was analyzed by gas chromatography. It is found that the 50% polymerization of leucine mixtures having excesses of 8 to 70% of either enantiomer leads to a significant enhancement of the enantiomeric excess of the polymer, accompanied by a corresponding decrease in the enantiomeric excess of the unpolymerized residue. On the other hand, 25-50% polymerization of valine mixtures is observed to result in polymers showing a decreased enantiomeric excess relative to the starting mixture and corresponding increases in those of the residue. Results of the leucine polymerization are interpreted as supporting the theory of steric interactions between the monomer and the helical structure of the polymer leading to the enrichment of one enantiomer, and possible mechanisms for the reverse stereospecificity observed in valine are discussed.

Blair, N. E.↗

NASA NTRS1980

Photochemical production of formaldehyde in earth's primitive atmosphere

Formaldehyde could have been produced by photochemical reactions in the earth's primitive atmosphere, at a time when it consisted mainly of molecular nitrogen, water vapor, carbon dioxide, and trace amounts of molecular hydrogen and carbon monoxide. Removal of formaldehyde from the atmosphere by precipitation can provide a source of organic carbon to the oceans at the rate of 100 billion moles per year. Subsequent reactions of formaldehyde in primeval aquatic environments would have implications for the abiotic synthesis of complex organic molecules and the origin of life.

Pinto, J. P.↗

NASA NTRS1981

Organic analysis of the Antarctic carbonaceous chondrites

Thus far, organic analysis of carbonaceous chondrites has proven the only fruitful means of examining complex organic matter of extraterrestrial origin. The present paper presents the results of organic analysis of two Antarctic meteorites, Allan Hills (77306) and Yamato (74662), which may be considered free from terrestrial contamination. Ion-exchange chromatography, gas chromatography and mass spectrometery of meteorite samples reveal the presence in Yamato of 15 and in Allan Hills of 20 protein and nonprotein amino acids, the most abundant of which are glycine and alanine. Abundances of the D and L enantiomers of each amino acid are also found to be nearly equal. Data thus indicate an abiotic extraterrestrial origin for the matter, and confirm a lack of terrestrial contamination.

Kotra, R. K.↗

NASA NTRS1981

Photoassisted carbon dioxide reduction and formation of twoand three-carbon compounds

The photoassisted reduction of aqueous carbon dioxide in the presence of naturally occurring minerals is investigated as a possible abiotic precursor of photosynthesis. Aqueous carbon dioxide saturated suspensions or surfaces of the minerals nontronite, bentonite, anatase, wolframite, molybdenite, minium, cinnabar and hematite were irradiated with high-pressure mercury lamps or sunlight. Chemical analyses reveal the production of formic acid, formaldehyde, methanol and methane, and the two and three-carbon compounds glyoxal (CHOCHO) and malonaldehyde (CH2(CHO)2). It is suggested that such photosynthetic reactions with visible light in the presence of semiconducting minerals may provide models for prebiological carbon and nitrogen fixation in both oxidized and reduced atmospheres.

Halmann, M.↗

NASA NTRS1981

Organic compounds in meteorites and their origins

The current investigation represents an extensively updated version of a review conducted by Anders et al. (1973). The investigation takes into account the literature through mid-1980. It is pointed out that Type 1 carbonaceous chondrites (C1) contain 6% of their cosmic complement of carbon, mainly in the form of organic matter. Most authors now agree that this material represents primitive prebiotic matter. The principal questions remaining are what abiotic processes formed the organic matter, and to what extent these processes took place in locales other than the solar nebula, such as interstellar clouds or meteorite parent bodes. The problem is approached in three stages. It is attempted to reconstruct the physical conditions during condensation from the clues contained in the inorganic matrix of the meteorite. The condensation behavior of carbon under these conditions is determined on the basis of thermodynamic calculations. Model experiments on the condensation of carbon are performed, and the synthesized compounds are compared with those actually found in meteorites.

Hayatsu, R.↗

NASA NTRS1983

Chemical evolution and the origin of life

A review is presented of recent advances made in the understanding of the formation of carbon compounds in the universe and the occurrence of processes of chemical evolution. Topics discussed include the principle of evolutionary continuity, evolution as a fundamental principle of the physical universe, the nuclear synthesis of biogenic elements, organic cosmochemistry and interstellar molecules, the solar nebula and the solar system in chemical evolution, the giant planets and Titan in chemical evolution, and comets and their interaction with the earth. Also examined are carbonaceous chondrites, environment of the primitive earth, energy sources available on the primitive earth, the synthesis of biochemical monomers and oligomers, the abiotic transcription of nucleotides, unified prebiotic and enzymatic mechanisms, phospholipids and membranes, and protobiological evolution.

Oro, J.↗

NASA NTRS1984

Inland Aquatic Resources and Biogeochemical Cycles

The biosphere is the entire planetary system that includes, sustains and is influenced by life. The central issue of the science of the biosphere is the extent to which the Earth's surface, atmosphere and hydrosphere is the result of biological rather than abiotic processes. Space science and technology accelerates the understanding of global biological processes by providing repetive synoptic observations on large spatial scales once the relationships between the processes and the remotely sensed quantities are established. Especially promising applications of space technology are the measurement of biological productivity and portions of geochemical cycles in aquatic ecosystems and the evaluation and management of the quality of freshwater resources.

Melack, J. M.↗