Studies on the Incorporation of Isotopically Labeled Nucleotides and Amino Acids in Planaria
Incorporation of isotopically labeled nucleotides and amino acids studies in planaria
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Molecular and mass spectroscopic analysis of isotopically labeled organic residues
Experimental studies aimed at understanding the evolution of complex organic molecules on interstellar grains were performed. The photolysis of frozen gas mixtures of various compositions containing H2O, CO, NH3, and CH4 was studied. These species were chosen because of their astrophysical importance as deducted from observational as well as theoretical studies of ice mantles on interstellar grains. These ultraviolet photolyzed ices were warmed up in order to produce refractory organic molecules like the ones formed in molecular clouds when the icy mantles are being irradiated and warmed up either by a nearby stellar source or impulsive heating. The laboratory studies give estimates of the efficiency of production of such organic material under interstellar conditions. It is shown that the gradual carbonization of organic mantles in the diffuse cloud phase leads to higher and higher visual absorptivity - yellow residues become brown in the laboratory. The obtained results can be applied to explaining the organic components of comets and their relevance to the origin of life.
Mendoza-Gomez, Celia X.↗
Comet Halley as an aggregate of interstellar dust and further evidence for the photochemical formation of organics in the interstellar medium
Photolysis of mixtures of CO:NH3:H2O at 12 K results in the formation of an organic residue which is not volatile in high vacuum at room temperature. Analysis of this fraction by GC-MS resulted in the detection of C2-C3 hydroxy acids and hydroxy amides, glycerol, urea, glycine, hexamethylene tetramine, formamidine and ethanolamine. Use of isotopically labeled gases made it possible to establish that the observed products were not contaminants. The reaction pathways for the formation of these products were determined from the position of the isotopic labels in the mass spectral fragments. The significance of these findings to the composition of comets and the origins of life is discussed.
Briggs, R.↗
Elucidation of the Cross-Link Structure of Nadic-End-Capped Polyimides Using NMR of C-13-Labeled Polymers
Solid NMR of C-13 isotope-labeled samples of PMR-15 was used to follow the cross-linking reaction of the nadic end cap. Some samples were labeled on one of the carbon atoms of the nadic end cap, and others on the methylene carbon atom of the methylenedianiline portion of the polymer. NMR spectra were run on these samples both before and after cross-linking. In this way, direct evidence of the major products of cross-linking under normal cure conditions is provided. The majority (approximately 85%) of the cross-linking derives from olefin polymerization through the double bond of the end cap. Approximately 15% of the products could come from a pathway involving a retro-Diels-Alder reaction. However, all of the products could be explained by a biradical intermediate without a retro-Diels-Alder reaction. Evidence is also presented that the methylene moiety in the methylenedianiline part of the polymer chain also participates in the cross-linking, albeit to a small extent, by a radical transfer reaction. Different cure conditions (higher temperatures, longer times) could change the relative distribution of the products.
Meador, Mary Ann B.↗
H, C, N, and O Isotopic Substitution Studies of the 2165 cm (4.62 micron) "XCN" Feature Produced by UV Photolysis of Mixed Molecular Ices
To better understand the chemical species that gives rise to the 2165/cm (4.62 micron) "XCN" absorption feature seen towards embedded protostars such as W33A, we have performed laboratory studies using deuterium (H-2) isotopic labeling. We report the observation of a small but significant deuterium isotope shift for the "XCN" peak which demonstrates that the atomic motion(s) causing the "XCN" band in the laboratory samples must involve hydrogen. We also report the results of C-13, N-15 and O-18 labeling experiments that are consistent with previously reported values.
Bernstein, Max P.↗
Mass spectrometry.
Review of the current state of mass spectrometry, indicating its unique importance for advanced scientific research. Mass spectrometry applications in computer techniques, gas chromatography, ion cyclotron resonance, molecular fragmentation and ionization, and isotope labeling are covered. Details are given on mass spectrometry applications in bio-organic chemistry and biomedical research. As the subjects of these applications are indicated alkaloids, carbohydrates, lipids, terpenes, quinones, nucleic acid components, peptides, antibiotics, and human and animal metabolisms. Particular attention is given to the mass spectra of organo-inorganic compounds, inorganic mass spectrometry, surface phenomena such as secondary ion and electron emission, and elemental and isotope analysis. Further topics include mass spectrometry in organic geochemistry, applications in geochronology and cosmochemistry, and organic mass spectrometry.
Burlingame, A. L.↗
Evidence for only minor contributions from bacteria to sedimentary organic carbon
Because their molecular signatures are often prominent in extracts of sediments, bacteria are thought to be important contributors to petroleum source beds. It has been shown recently, however, that abundances of biomarkers do not always reflect relative contributions to sedimentary organic carbon (Corg). The contribution of photosynthetic green sulphur bacteria to sediments can be assessed effectively because the diagenetic products of distinctive carotenoids from these organisms occur widely and their biomass is isotopically labelled, being enriched in 13C. We show here that, although sediments and oils from the Western Canada and Williston basins contain prominent biomarkers of photosynthetic bacteria, the absence of 13C enrichment in the total Corg requires that the bacterial contribution is in fact minimal. Although the importance of bacterial reworking of sedimentary debris cannot be doubted, we argue that our findings, when considered in conjunction with those from other settings, suggest that bacterial biomass may commonly represent only a minor component of total Corg in carbonaceous rocks.
NASA Discipline Exobiology↗
Mass spectrometry in structural and stereochemical problems. CXLIV - Unusual fragmentations in the low-voltage spectra of aliphatic ketones.
Mass spectra of isotopically labeled aliphatic ketones at low voltage, showing deuterium scrambling among alyphatic carbon atoms
Carpenter, W.↗
High resolution mass spectrometry in molecular studies. XVII.
Ring contractions in molecular ions as mechanism of N-acetylmorpholine electron impact fragmentation, using high resolution mass spectrometry and isotopic labeling
Burlingame, A. L.↗
Compartmentation of glutamic acid metabolism in brain slices.
Glutamic acid metabolism compartmentation in brain cortex demonstrated in vitro, using isotopic labeling
Berl, S.↗
Stress corrosion in titanium alloys and other metallic materials
Multiple physical and chemical techniques including mass spectroscopy, atomic absorption spectroscopy, gas chromatography, electron microscopy, optical microscopy, electronic spectroscopy for chemical analysis (ESCA), infrared spectroscopy, nuclear magnetic resonance (NMR), X-ray analysis, conductivity, and isotopic labeling were used in investigating the atomic interactions between organic environments and titanium and titanium oxide surfaces. Key anhydrous environments studied included alcohols, which contain hydrogen; carbon tetrachloride, which does not contain hydrogen; and mixtures of alcohols and halocarbons. Effects of dissolved salts in alcohols were also studied. This program emphasized experiments designed to delineate the conditions necessary rather than sufficient for initiation processes and for propagation processes in Ti SCC.
Harkins, C. G.↗
Reaction between nitric oxide and ozone in solid nitrogen
Nitrogen dioxide, NO2, is produced when nitric oxide, NO, and ozone, O3, are suspended in a nitrogen matrix at 11-20 K. The NO2 is formed with first-order kinetics, a 12 K rate constant of (1.4 + or - 0.2) x 0.00001/sec, and an apparent activation energy of 106 + or - 10 cal/mol. Isotopic labeling, variation of concentrations, and cold shield experiments show that the growth of NO2 is due to reaction between ozone molecules and NO monomers, and that the reaction is neither infrared-induced nor does it seem to be a heavy atom tunneling process. Reaction is attributed to nearest-neighbor NO.O3 pairs probably held in a specific orientational relationship that affects the kinetic behavior. When the temperature is raised, more such reactive pairs are generated, presumably by local diffusion. Possible mechanisms are discussed.
Lucas, D.↗
Laboratory studies of the kinetics of tropospheric and stratospheric atom and radical reactions
Direct measurements of reaction rate constants and branching fractions for elementary reactions necessary in the modeling of the troposphere or stratosphere are provided. Details of reaction mechanisms are elucidated by studying pressure and temperature dependences of reactions, as well as by use of isotopic labels. Measurement techniques are improved for radical species in the laboratory. Progress and results in each area are given.
Golde, Michael F.↗
On the possible role of the reaction O + HO2 - OH + O2 in OH airglow
Experimental data on the so-called 'perhydroxyl' reaction O + HO2 - OH + O2 by which vibrationally excited OH is produced in the upper atmosphere are briefly reviewed. Both isotopic labeling studies and studies on the temperature dependence of the rate constant and the possible importance of its inverse are considered. The implication of the results for analysis of OH airglow data are emphasized. Some additional results on the dynamics of reactions related to OH airglow which may affect interpretation of OH emission measurements are summarized.
Kaye, Jack A.↗
Laboratory shock emplacement of noble gases, nitrogen, and carbon dioxide into basalt, and implications for trapped gases in shergottite EETA 79001
Basalts from the Servilleta flows, Taos, NM, described by Lofgren (1983) were analyzed by mass spectrometry for shock-implanted noble gases, N2, and CO2 (which were isotopically labeled) after an exposure to 20-60 GPa shock in the presence of 0.0045-3.0 atm of ambient gas. The results were compared with data available on the constituents of the EETA 79001 meteorite. As expected, the samples shocked in this study attained emplacement efficiencies significantly lower than those apparent for lithology C of EETA 79001. Possible explanations for this difference include atmospheric overpressure at the time of EETA 79001 exposure to shock, the trapping of gas already in vugs by the intruding melt material, or the collapse of gas-filled vugs to form gas-laden glass inclusions.
Wiens, R. C.↗
A mass spectrometric study of the simultaneous reaction mechanism of TMIn and PH3 to grow InP
The reaction mechanisms for the growth of InP from various mixtures of trimethyl indium (TMIn) and PH3 by OMVPE were investigated using mass spectrometry and a D2 ambient for isotopic labeling of the reaction products. It was found that, whereas TMIn alone pyrolyzes homogeneously, forming CH3D, and PH3 alone pyrolyzes heterogeneously, producing H2, the pyrolysis reactions of TMIn and PH3 together are completely different. The pyrolysis temperatures of both TMIn and PH3 are reduced (by 50 C for TMIn and 225 C for PH3), and the sole product is CH4 at high values of the PH3/TMIn ratio. The pyrolysis reaction is shown to be coupled (as evidenced by the equal depletion of TMIn and PH3 from the vapor) and, at temperatures below 400 C, heterogeneous.
Buchan, N. I.↗
Rare-isotope and kinetic studies of Pt/SnO2 catalysts
Closed-cycle pulsed CO2 laser operation requires the use of an efficient CO-O2 recombination catalyst for these dissociation products which otherwise would degrade the laser operation. The catalyst must not only operate at low temperatures but also must operate efficiently for long periods. In the case of the Laser Atmospheric Wind Sounder (LAWS) laser, an operational lifetime of 3 years is required. Additionally, in order to minimize atmospheric absorption and enhance aerosol scatter of laser radiation, the LAWS system will operate at 9.1 micrometers with an oxygen-18 isotope CO2 lasing medium. Consequently, the catalyst must not only operate at low temperatures but must also preserve the isotopic integrity of the rare-isotope composition in the recombination mode. Several years ago an investigation of commercially available and newly synthesized recombination catalysts for use in closed-cycle pulsed common and rare-isotope CO2 lasers was implemented at the NASA Langley Research Center. Since that time, mechanistic efforts utilizing both common and rare oxygen isotopes have been implemented and continue. Rare-isotope studies utilizing commercially available platinum-tin oxide catalyst have demonstrated that the catalyst contributes oxygen-16 to the product carbon dioxide thus rendering it unusable for rare-isotope applications. A technique has been developed for modification of the surface of the common-isotope catalyst to render it usable. Results of kinetic and isotope label studies using plug flow, recycle plug flow, and closed internal recycle plug flow reactor configuration modes are discussed.
Upchurch, Billy T.↗
New insights in the photochemistry of grain mantles: The identification of the 4.62 and 6.87 micron bands
The mid-IR spectral region of molecular clouds is known to show the fingerprints of molecules frozen in the icy mantles of the interstellar grains. To study the complex chemical and physical interactions on the ice mantles accreted on grains in molecular clouds numerous UV irradiation and diffusion experiments were performed. The irradiation of binary ices was studied. Using isotopic labelling on NH3/CO and NH3/O2 ices numerous compounds were identified, of which OCN(-), NO2(-), NO3(-), and NH4(+) ions reveal a new type of chemical reactions. It appeared that these compounds were formed by proton transfer reactions induced by the interaction between an acid (HNCO, HNO2, HNO3) and a base (NH3) through a hydrogen bond. This mechanism was confirmed by a study of photolyzed diluted argon mixtures. The main astrophysically relevant data from the overall study are presented. The 4.62 micron band in W33A can be reproduced with NH3/CO containing irradiated ices and was identified with OCN(-). The 6.87 micron band in W33A and other photostellar objects is reproduced with NH3/O2 containing ices and is identified with NH4(+).
Grim, Ruud↗