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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1974

The determination of ethanol in blood and urine by mass fragmentography

A mass fragmentographic technique for a rapid, specific and sensitive determination of ethanol in blood and urine is described. A Varian gas chromatograph coupled through an all-glass membrane separator to a Finnigan quadripole mass spectrometer and interfaced to a computer system is used for ethanol determination in blood and urine samples. A procedure for plotting calibration curves for ethanol quantitation is also described. Quantitation is achieved by plotting the peak area ratios of undeuterated-to-deuterated ethanol fragment ions against the amount of ethanol added. Representative results obtained by this technique are included.

Pereira, W. E.↗
NASA NTRS1972

The simultaneous quantitation of ten amino acids in soil extracts by mass fragmentography

A specific and sensitive method for the identification and simultaneous quantitation by mass fragmentography of ten of the amino acids present in soil was developed. The technique uses a computer driven quadrupole mass spectrometer and a commercial preparation of deuterated amino acids is used as internal standards for purposes of quantitation. The results obtained are comparable with those from an amino acid analyzer. In the quadrupole mass spectrometer-computer system up to 25 pre-selected ions may be monitored sequentially. This allows a maximum of 12 different amino acids (one specific ion in each of the undeuterated and deuterated amino acid spectra) to be quantitated. The method is relatively rapid (analysis time of approximately one hour) and is capable of the quantitation of nanogram quantities of amino acids.

Pereira, W. E.↗
NASA NTRS1974

Analysis of twelve amino acids in biological fluids by mass fragmentography

Description of a computerized method for the simultaneous quantitation of 12 amino acids in biological fluids using the technique of quadrupole mass in fragmentography. The time taken for one complete analysis, exclusive of derivatization, is 40 minutes for data collection with an additional 10 minutes before the computer presents the final analytical result.

Summons, R. E.↗
NASA NTRS1972

Cytochemical studies of planetary microorganisms - Explorations in exobiology

Analytical methodology using gas chromatography and mass spectrography for improved physiological monitoring of astronauts is developed. Reported research covers the following topics: (1) Chlorination of DNA bases; (2) mass fragmentography; (3) mass spectrometry; (4) urine analysis for metabolic constituents; (5) analysis of natural products by mass spectrometry; (6) computer identification of unknown molecular compounds; (7) fluorescent sorter for cell separation; (8) Mariner Mars 1971 orbital photography; and (9) Viking Lander imagery.

Lederberg, J.↗
NASA NTRS1976

Mass spectrometry

Advances in mass spectrometry (MS) and its applications over the past decade are reviewed in depth, with annotated literature references. New instrumentation and techniques surveyed include: modulated-beam MS, chromatographic MS on-line computer techniques, digital computer-compatible quadrupole MS, selected ion monitoring (mass fragmentography), and computer-aided management of MS data and interpretation. Areas of application surveyed include: organic MS and electron impact MS, field ionization kinetics, appearance potentials, translational energy release, studies of metastable species, photoionization, calculations of molecular orbitals, chemical kinetics, field desorption MS, high pressure MS, ion cyclotron resonance, biochemistry, medical/clinical chemistry, pharmacology, and environmental chemistry and pollution studies.

Burlingame, A. L.↗
NASA NTRS1981

Quantification of monocarboxylic acids from a spark discharge synthesis

A suite of sixteen monocarboxylic acids having carbon numbers 2 to 7, formed by the Miller-Urey spark discharge process, was identified and quantified by gas chromatography and mass fragmentography using a deuterium spiking technique. The molar concentration and isomeric distribution of these laboratory synthesized monocarboxylic acids are compared to those previously reported for the Murchison meteorite. They show similar trends, namely, decreasing molar concentration with increasing molecular weight, and a ratio of normal/branched isomers tending toward smaller values with increasing carbon numbers.

Yuen, G. U.↗
NASA NTRS2001

Carbonaceous meteorites as a source of sugar-related organic compounds for the early Earth

The much-studied Murchison meteorite is generally used as the standard reference for organic compounds in extraterrestrial material. Amino acids and other organic compounds important in contemporary biochemistry are thought to have been delivered to the early Earth by asteroids and comets, where they may have played a role in the origin of life. Polyhydroxylated compounds (polyols) such as sugars, sugar alcohols and sugar acids are vital to all known lifeforms-they are components of nucleic acids (RNA, DNA), cell membranes and also act as energy sources. But there has hitherto been no conclusive evidence for the existence of polyols in meteorites, leaving a gap in our understanding of the origins of biologically important organic compounds on Earth. Here we report that a variety of polyols are present in, and indigenous to, the Murchison and Murray meteorites in amounts comparable to amino acids. Analyses of water extracts indicate that extraterrestrial processes including photolysis and formaldehyde chemistry could account for the observed compounds. We conclude from this that polyols were present on the early Earth and therefore at least available for incorporation into the first forms of life.

Biogenesis↗
NASA NTRS1998

Nitrogen recycling during phenylpropanoid metabolism in sweet potato tubers

In the first step of the phenylpropanoid metabolic pathway, L-phenylalanine (L-Phe) is deaminated to form E-cinnamate, in a conversion catalyzed by phenylalanine ammonia-lyase (PAL; EC 4.3.1.5). The metabolic fate of the ammonium ion (NH4+) produced in this reaction was investigated in sweet potato (Ipomoea batatas) tuber discs. [15N]-Labeled substrates including L-Phe, in the presence or absence of specific enzyme inhibitors, were administered to sweet potato discs in light under aseptic conditions. 15N-Nuclear magnetic resonance spectroscopic analyses revealed that the 15NH4+ liberated during the PAL reaction is first incorporated into the amide nitrogen of L-glutamine (L-Gln) and then into L-glutamate (L-Glu). These results extend our previous observations in pine and potato that PAL-generated NH4+ is assimilated by the glutamine synthetase (GS; EC 6.3.1.2)/glutamate synthase (GOGAT; EC 1.4.1.13) pathway, with the NH4+ so formed ultimately being recycled back to L-Phe via L-Glu as aminoreceptor and donor.

Non-NASA Center↗
NASA NTRS1998

Kinetic preference for the 3'-5'-linked dimer in the reaction of guanosine 5'-phosphorylmorpholinamide with deoxyguanosine 5'-phosphoryl-2-methylimidazolide as a function of poly(C) concentration

The formation of the internucleotide bond in diguanylate synthesis was studied in aqueous solution at pH 8 and 0.2 M Mg2+ in the presence and absence of polycytidylate, poly(C). The investigation was simplified by using guanosine 5'-phosphorylmorpholinamide, mor-pG, which can act only as a nucleophile, and deoxyguanosine 5'-phosphoryl-2-methylimidazolide, 2-MeImpdG, which can act only as an electrophile. The time-dependent product distribution was monitored by high-performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC/MS). In the absence of poly(C) the reaction between mor-pG and 2-MeImpdG yielded small amounts of the dimer mor-pGpdG with a regioselectivity of 2'-5':3'-5' = 3.5. In the presence of poly(C) dimer yields increased and a reversal in regioselectivity occurred; both effects were in proportion to the concentration of the polymer. The results can be quantitatively explained with the proposition that poly(C), acting as the template, catalyzes the reaction between template-bound monomers by about a factor of 4-5 over the reaction in solution and yields dimers with a regioselectivity of 2'-5':3'-5' approximately 0.33. These findings illustrate the intrinsic preference of guanosine monomers to correctly self-assemble on the appropriate template.

NASA Discipline Exobiology↗
NASA NTRS1996

Phenols in hydrothermal petroleums and sediment bitumen from Guaymas Basin, Gulf of California

The aliphatic, aromatic and polar (NSO) fractions of seabed petroleums and sediment bitumen extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry (free and silylated). The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolyzates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore sediments are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds in samples with a high degree of thermal maturity. Phenols are one class of oxygenated compounds found in these samples. A group of methyl-, dimethyl- and trimethyl-isoprenoidyl phenols (C27-C29) is present in all of the seabed NSO fractions, with the methyl- and dimethyl-isoprenoidyl phenols occurring as major components, and a trimethyl-isoprenoidyl phenol as a minor component. A homologous series of n-alkylphenols (C13-C33) has also been found in the seabed petroleums. These phenols are most likely derived from the hydrothermal alteration of sedimentary organic matter. The n-alkylphenols are probably synthesized under hydrothermal conditions, but the isoprenoidyl phenols are probably hydrothermal alteration products of natural product precursors. The suites of phenols do not appear to be useful tracers of high temperature hydrothermal processes.

Non-NASA Center↗
NASA NTRS1997

Experimental indication of a naphthalene-base molecular aggregate for the carrier of the 2175 angstroms interstellar extinction feature

Experiments where the simple polycyclic aromatic hydrocarbon (PAH) naphthalene (C10H8) is subjected to the energetic environment of a plasma have resulted in the synthesis of a molecular aggregate that has ultraviolet spectral characteristics that suggest it provides insight into the nature of the carrier of the 2175 angstroms interstellar extinction feature and may be a laboratory analog. Ultraviolet, visible, infrared, and mass spectroscopy, along with gas chromatography, indicate that it is a molecular aggregate in which an aromatic double ring ("naphthalene") structural base serves as the electron "box" chromophore that gives rise to the envelope of the 2175 angstroms feature. This chromophore can also provide the peak of the feature or function as a mantle in concert with another peak provider such as graphite. The molecular base/chromophore manifests itself both as a structural component of an alkyl-aromatic polymer and as a substructure of hydrogenated PAH species. Its spectral and molecular characteristics are consistent with what is generally expected for a complex molecular aggregate that has a role as an interstellar constituent.

NASA Discipline Exobiology↗
NASA NTRS1995

Plasma processing of interstellar PAHs into solar system kerogen

Processes resulting in the formation of hydrocarbons of carbonaceous chondrites and the identity of the interstellar molecular precursors involved are an objective of investigations into the origin of the solar system and perhaps even life on earth. We have combined the resources and experience of an astronomer and physicists doing laboratory simulations with those of a chemical expert in the analysis of meteoritic hydrocarbons, in a project that investigated the conversion of polycyclic aromatic hydrocarbons (PAHs) formed in stellar atmospheres into alkanes found in meteorites. Plasma hydrogenation has been found in the University of Alabama at Birmingham Astrophysics Laboratory to produce from the precursor PAH naphthalene, a new material having an IR absorption spectrum (Lee, W. and Wdowiak, T.J., Astrophys. J. 417, L49-L51, 1993) remarkably similar to that obtained at Arizona State University of the benzene-methanol extract of the Murchison meteorite (Cronin, J.R. and Pizzarello, S., Geochim. Cosmochim. Acta 54, 2859-2868, 1990). There are astrophysical and meteoritic arguments for PAH species from extra-solar sources being incorporated into the solar nebula, where plasma hydrogenation is highly plausible. Conversion of PAHs into alkanes could also have occurred in the interstellar medium. The synthesis of laboratory analogs of meteoritic hydrocarbons through plasma hydrogenation of PAH species is underway, as is chemical analysis of those analogs. The objective is to clarify this heretofore uninvestigated process and to understand its role during the origin of the solar system as a mechanism of production of hydrocarbon species now found in meteorites. Results have been obtained in the form of time-of-flight spectroscopy and chemical analysis of the lab analog prepared from naphthalene.

NASA Discipline Exobiology↗
NASA NTRS1994

A molecular and isotopic study of the organic matter from the Paris Basin, France

Thirteen Liassic sedimentary rocks of increasing depth and three petroleums from the Paris Basin were studied for 13C/12C isotopic compositions and biological markers, including steranes, sterenes, methylphenanthrenes, methylanthracenes, and triaromatic steroids. The isotopic compositions of n-alkanes from mature sedimentary rocks and petroleums fall in a narrow range (2%), except for the deepest Hettangian rock and the Trias petroleum, for which the short-chain n-alkanes are enriched and depleted in 13C, respectively. Most of the molecular parameters increase over the 2000-2500 m depth range, reflecting the transformation of the organic matter at the onset of petroleum generation. In this zone, carbonate content and carbon isotopic composition of carbonates, as well as molecular parameters, are distinct for the Toarcian and Hettangian source rocks and suggest a migration of organic matter from these two formations. Two novel molecular parameters were defined for this task: one using methyltriaromatic steroids from organic extracts; the other using 1-methylphenanthrene and 2-methylanthracene from kerogen pyrolysates. The anomalous high maturity of the Dogger petroleum relative to the maturity-depth trend of the source rocks is used to estimate the minimal vertical distance of migration of the organic matter from the source rock to the reservoir.

Non-NASA Center↗
NASA NTRS1994

Predictive isotopic biogeochemistry: hydrocarbons from anoxic marine basins

Carbon isotopic compositions were determined for individual hydrocarbons in water column and sediment samples from the Cariaco Trench and Black Sea. In order to identify hydrocarbons derived from phytoplankton, the isotopic compositions expected for biomass of autotrophic organisms living in surface waters of both localities were calculated based on the concentrations of CO2(aq) and the isotopic compositions of dissolved inorganic carbon. These calculated values are compared to measured delta values for particulate organic carbon and for individual hydrocarbon compounds. Specifically, we find that lycopane is probably derived from phytoplankton and that diploptene is derived from the lipids of chemoautotrophs living above the oxic/anoxic boundary. Three acyclic isoprenoids that have been considered markers for methanogens, pentamethyleicosane and two hydrogenated squalenes, have different delta values and apparently do not derive from a common source. Based on the concentration profiles and isotopic compositions, the C31 and C33 n-alkanes and n-alkenes have a similar source, and both may have a planktonic origin. If so, previously assigned terrestrial origins of organic matter in some Black Sea sediments may be erroneous.

Non-NASA Center↗
NASA NTRS1996

A system and methodology for measuring volatile organic compounds produced by hydroponic lettuce in a controlled environment

A system and methodology were developed for the nondestructive qualitative and quantitative analysis of volatile emissions from hydroponically grown 'Waldmann's Green' leaf lettuce (Lactuca sativa L.). Photosynthetic photon flux (PPF), photoperiod, and temperature were automatically controlled and monitored in a growth chamber modified for the collection of plant volatiles. The lipoxygenase pathway products (Z)-3-hexenal, (Z)-3-hexenol, and (Z)-3-hexenyl acetate were emitted by lettuce plants after the transition from the light period to the dark period. The volatile collection system developed in this study enabled measurements of volatiles emitted by intact plants, from planting to harvest, under controlled environmental conditions.

NASA Discipline Life Support Systems↗