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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
NASA NTRS1983

Latitudinal distributions and temporal changes of stratospheric HCl and HF

Hydrogen chloride and hydrogen fluoride are important sinks in the stratosphere for free halogens. The major sources of chlorine and fluorine in the stratosphere are anthropogenic; therefore, a measurement of HCl and HF gives information about the magnitude of anthropogenic effects on stratospheric chemistry and may give some information about the stratospheric hydroxyl concentration as well. The total column amount of HCl and HF above 12 km has been determined by measuring infrared absorption spectra with a high-resolution Fourier transform spectrometer flown on a jet aircraft. The HCl column varies from 0.7 x 10 to the 15th molecules/ sq cm near the equator to 2.7 x 10 to the 15th molecules/sq cm at 70 N; the HF column is about a factor of 5 lower. The HCl:HF ratio is almost independent of latitude, and neither constituent shows substantial seasonal or diurnal variation. At mid-latitudes, the data from 1978 to 1982 show an annual increase of 5 percent per year for HCl and 12 percent per year for HF.

Mankin, W. G.↗
NASA NTRS1984

Carbon monoxide in the earth's atmosphere - Increasing trend

The results of an analysis of more than 60,000 atmospheric measurements of carbon monoxide taken over 3-1/2 years at Cape Meares, Oregon (45 deg N, 125 deg W), indicate that the background concentration of this gas is increasing. The rate of increase, although uncertain, is about 6 percent per year on average. Human activities are the likely cause of a substantial portion of this observed increase; however, because of the short atmospheric lifetime of carbon monoxide and the relatively few years of observations, fluctuations of sources and sinks related to the natural variability of climate may have affected the observed trend. Increased carbon monoxide may deplete tropospheric hydroxyl radicals, slowing down the removal of dozens of man-made and anthropogenic trace gases and thus indirectly affecting the earth's climate and possibly the stratospheric ozone layer.

Khalil, M. A. K.↗
NASA NTRS1984

The prebiotic chemistry of nucleotides

Diminosuccinonitrile (DISN), formed by the oxidation of diaminomaleonitrile, has been investigated as a potential prebiotic phosphorylating agent. DISN affects the cyclization of 3'-adenosine monophosphate to adenosine 2',3'-cyclic phosphate in up to 39 percent yield. The mechanism of this reaction was investigated. The DISN-mediated phosphorylation of uridine to uridine monophosphate does not proceed efficiencly in aqueous solution. The reaction of DISN with uridine-5'-phosphate and uridine results in the formation of 2,2'-anhydronucleotides and 2,2'-anhydronucleosides respectively, and other reaction products resulting from an initial reaction at the 2'- and 3'-hydroxyl groups. The clay mineral catalysis of the cyclization of adenosine-3'-phosphate was investigated using homoionic montmorillonites.

Ferris, J. P.↗
NASA NTRS1984

Nucleic acids, proteins, and chirality

The present investigation is concerned with experimental results related, in one case, to the chirality of nucleotides, and, in another case, to the possibility of a link between the chirality of nucleic acids, and that of peptides. It has been found that aminoacylation of the 'internal' hydroxyl group of a dinucleoside monophosphate can occur stereoselectively. However, this reaction has not yet been made a part of a working peptide synthesis scheme. The formation and cleavage of oligonucleotides is considered. In the event of the formation of a helical complex between the oligonucleotide and the polymer, 1-prime,5-prime-bonds in the oligomer are found to become more resistant towards cleavage. The conditions required for peptide bond formation are examined, taking into account the known structures of RNA and possible mechanisms for prebiotic peptide bond formation. The possibility is considered that the 2-prime,5-prime-internucleotide linkage could have played an important part in the early days of biological peptide synthesis.

Usher, D. A.↗
NASA NTRS1984

Hydrogen atom abstraction from aldehydes - OH + H2CO and O + H2CO

The essential features of the potential energy surfaces governing hydrogen abstraction from formaldehyde by oxygen atom and hydroxyl radical have been characterized with ab inito multiconfiguration Hartree-Fock (MCHF) and configuration interaction (CI) wave functions. The results are consistent with a very small activation energy for the OH + H2CO reaction, and an activation energy of a few kcal/mol for the O + H2CO reaction. In the transition state structure of both systems, the attacking oxygen atom is nearly collinear with the attacked CH bond.

Dupuis, M.↗
NASA NTRS1984

Stereoselective aminoacylation of a dinucleoside monophosphate by the imidazolides of DL-alanine and N-(tert-butoxycarbonyl)-DL-alanine

The aminoacylation of diinosine monophosphate was studied experimentally. When the acylating agent was the imidazolide of N-(tert-butoxycarbonyl)-DL-alanine, a 40 percent enantiomeric excess of the isomer was incorporated at the 2' site and the positions of equilibrium for the reversible 2'-3' migration reaction differed for the D and L enantiomers. The reactivity of the nucleoside hydroxyl groups was found to decrease on the order 2'(3') less than internal 2' and less than 5', and the extent of the reaction was affected by the concentration of the imidazole buffer. Reaction of IpI with imidazolide of unprotected DL-alanine, by contrast, led to an excess of the D isomer at the internal 2' site. Finally, reaction with the N-carboxy anhydride of DL-alanine occurred without stereoselection. These results are found to be relevant to the study of the evolution of optical chemical activity and the origin of genetically directed protein synthesis.

Profy, A. T.↗
NASA NTRS1984

Tropospheric methane in the mid-latitudes of the Southern Hemisphere

More than 800 methane concentration measurements have been obtained for the Southern Hemisphere's troposphere over the September 1980-March 1983 period. Concentrations are noted to increase throughout the troposphere during the study period, adding further support to the view that CH4 concentrations are currently increasing on a global scale. In the surface methane data, a seasonal cycle with a peak-to-peak amplitude of 28 ppbv is found. Maxima and minima are on September-October and March, respectively. The phase and amplitude of the cycle are qualitatively consistent with the concept that the major sink for methane is oxidation by hydroxyl radicals. Evidence is found for a positive vertical gradient in methane content.

Fraser, P. J.↗
NASA NTRS1984

Landsat-4 thematic mapper and thematic mapper simulator data for a porphyry copper deposit

Aircraft thematic mapper (TM) data were analyzed to evaluate the potential utility of the Landsat-4 thematic mapper for geologic mapping and detection of hydrothermal alteration zones in the Silver Bell porphyry copper deposit in southern Arizona. The data allow a comparison between aircraft TV simulator data and the Landsat-4 TM satellite data which possess similar spectral bands. A color rationcomposite of 30-m pixels was resampled, in order to clearly define a number of hydroxyl bearing minerals, (kaolinite, sericite, white mica), pyrite and iron oxide/hydroxide minerals. The iron oxide minerals have diagnostic absorption bands in the 0.45 and 0.85 micron regions of the spectrum, and the hydrous minerals are characterized by an absorption in the 2.2 micron region. The position of the spectral bands allow the TM to identify regions of hydrothermal alteration without resorting to a data processing algorithm. The comparison of the aircraft and Landsat-4 TM data showed considerable agreement, and confirmed the utility of TM data for identifying hydrothermal alteration zones. Samples of some color TM images are provided.

Abrams, M. J.↗
NASA NTRS1986

Chromium Ions Improve Moisure Resistance of Epoxy Resins

Broad spectrum of thermosetting epoxy resins used on commercial and military aircraft, primarily as composite matrices and adhesives. In new technique, chromium-ion containing epoxy with improved resistance to moisture produced where chromium ions believed to prevent absorption of water molecules by coordinating themselves to hydroxyl groups on epoxy chain. Anticipated that improved epoxy formulation useful as composite matrix resin, adhesive, or casting resin for applications on commercial and advanced aircraft. Improvement made without sacrifice in mechanical properties of polymer.

St. Clair, A. K.↗
NASA NTRS1985

First Direct Detection of Clay Minerals on Mars

Magnesian clays or clay-type minerals were conclusively detected in the martian regolith. Near-IR spectral observations of Mars using the Mauna Kea 2.2-m telescope show weak but definite absorption bands near microns. The absorption band positions and widths match those produced by combined OH stretch and Mg-OH lattice modes and are diagnostic of minerals with structural OH such as clays and amphiboles. Likely candidate minerals include serpentine, talc, hectorite, and sponite. There is no spectral evidence for aluminous hydroxylated minerals. No distinct band occurs at 2.55 microns, as would be expected if carbonates were responsible for the 2.35 micron absorption. High-albedo regions such as Elysium and Utopia have the strongest bands near 2.35 microns, as would be expected for heavily weathered soils. Low-albedo regions such as Iapygia show weaker but distinct bands, consistent with moderate coatings, streaks, and splotches of bright weathered material. In all areas observed, the 2.35-micron absorption is at least three times weaker than would be expected if well-crystallized clay minerals made up the bulk of bright soils on Mars.

Singer, R. B.↗
NASA NTRS1985

Spectroscopic analysis of radiation-generated changes in tensile properties of a polyetherimide film

The effects of electron radiation on Ultem, a polyetherimide were studied for doses from 2 x 10 to the 9th power to 6 x 10 to the 9th power rad. Specimens were studied for tensile property testing and for electron paramagnetic resonance and infrared spectroscopic measurements of molecular structure. A Faraday cup design and a method for remote temperature measurement were developed. The spectroscopic data show that radiation caused dehydrogenation of methyl groups, rupture of main-chain ether linkage, and opening of imide rings, all to form radicals and indicate that the so-formed atomic hydrogen attached to phenyl radicals, but not to phenoxyl radicals, which would have formed hydroxyls. The observed decays of the radiation-generated phenoxyl, gem-dimethyl, and carbonyl radicals were interpreted as a combining of the radicals to form crosslinking. This crosslinking is the probable cause of the major reduction in the elongation of the tensile specimens after irradiation. Subsequent classical solubility tests indicate that the irradiation caused massive crosslinking.

Long, E. R., Jr.↗
NASA NTRS1984

Water and the photochemistry of the troposphere

A discussion is presented concerning the role of water in its liquid and gaseous states in the chemistry and photochemistry of the earth's troposphere, with attention to the formation of the hydroxyl radical, oxidation chains involving the gases methane, carbon monoxide and ammonia, the atmospheric chemistry of the sulfur, hydrogen, halogen and nitrogen species, and the function of lightning as a source of tropospheric species. The phenomena of 'rainout', 'washout', and the aqueous chemistry of cloud an rain droplets and of water-covered aerosols, are noted. A section is devoted to the past and anticipated impact of anthropogenic activities on the chemistry and composition of the earth's atmosphere.

Levine, J. S.↗
NASA NTRS1984

The atmospheric lifetime of methylchloroform (CH3CCl3)

The lifetime of atmospheric methylchloroform (CH3CCl3) is estimated to be about 6 (+ or - 1.5) years based on extensive measurements taken over the past seven years at remote locations of the world, ranging from inside the Arctic Circle to the South Pole. The average level of tropospheric hydroxyl radicals (OH) deduced from the lifetime of CH3CCl3 is about 8 x 10 to the 5th molecules/cu cm, but this value is uncertain by up to + or - 75 percent.

Khalil, M. A. K.↗
NASA NTRS1985

Photodissociation rates of OH, OD, and CN by the interstellar radiation field

The photoabsorption cross sections for OH, OD, and CN in the vacuum ultraviolet region are measured. The cross sections for the hydroxyl radicals are of the order of 10 to the -17th sq cm, but the photoabsorption for CN is so low that only an upper limit of 2 x 10 to the -18th sq cm is obtained. The molecular photodissociative processes are discussed. The photodissociation cross sections are inferred from the photoabsorption cross sections. On the basis of the measured data, the photodissociation rates by the interstellar radiation field are computed and discussed.

Nee, J. B.↗
NASA NTRS1984

On the stereoselective aminoacylation of RNA

Gabbay and Kleinman (1970) have found that stereospecific complex formation (noncovalent) occurs between nucleic acids and a number of derivatives of amino acids. However, until recently, chiral selection in any nonenzymatic RNA-aminoacylation reaction was unknown. Profy and Usher (1984) reported that aminoacylation of the 'internal' 2-prime-ester occurred with a significant amount of stereoselection. Profy and Usher (1984) have also observed that aminoacylation of the 'internal' 2-prime-hydroxyl groups of polyribonucleotides by the imidazolide of N-3,5-dinitrobenzoylalanine occurs with chiral selection. In order to obtain further information regarding the considered phenomena, a systematic investigation was initiated of the factors which contribute to the observed stereoselectivity of the aminoacylation reaction. In the present paper, the effect of a change in the amino acid from alanine to leucine is considered along with an investigation of the D- and L-alanyl internal' 2-prime esters of the dinucleoside monophosphate of 3-prime,5-prime-ApA.

Usher, D. A.↗
NASA NTRS1985

Interstellar dust spectra between 2.5 and 3.3 microns - A search for hydrated silicates

Spectra in the 2.5-3.3 micron wavelength region of VI Cyg 12, AFGL 2205, and AFGL 2885 were obtained in a search for bound water, hydroxyl groups, and hydrated minerals in interstellar dust. No new absorption bands were found. Comparison of expected strengths of bands of serpentine and chlorite-like minerals with the data suggests that less than 25 percent and 50 percent, respectively, of the silicate in the grains is composed of these materials.

Knacke, R. F.↗
NASA NTRS1984

Mechanism for forming hydrogen chloride and sodium sulfate from sulfur trioxide, water, and sodium chloride

A molecular orbital study of sodium sulfate and hydrogen chloride formation from sulfur trioxide, water, and sodium chloride shows no activation barrier, in agreement with recent experimental work of Kohl, Fielder, and Stearns. Two overall steps are found for the process. First, gas-phase water reacts with sulfur trioxide along a pathway involving a linear O-H-O transition state yielding closely associated hydroxyl and bisulfite which rearrange to become a hydrogen sulfate molecule. Then the hydrogen sulfate molecule transfers a hydrogen atom to a surface chloride in solid sodium chloride while an electron and a sodium cation simultaneously transfer to yield sodium bisulfate and gas-phase hydrogen chloride. This process repeats. Both of these steps represent well-known reactions for which mechanisms have not been previously determined.

Anderson, A. B.↗
NASA NTRS1986

The production of trace gases by photochemistry and lightning in the early atmosphere

Recent atmospheric calculation suggest that the prebiological atmosphere was most probably composed of nitrogen, carbon dioxide, and water vapor, resulting from volatile outgassing, as opposed to the older view of a strongly reducing early atmosphere composed of methane, ammonia, and hydrogen. Photochemical calculations indicate that methane would have been readily destroyed via reaction with the hydroxyl radical produced from water vapor and that ammonia would have been readily lost via photolysis and rainout. The rapid loss of methane and ammonia, coupled with the absence of a significant source of these gases, suggest that atmospheric methane and ammonia were very short lived, if they were present at all. An early atmosphere of N2, CO2, and H2O is stable and leads to the chemical production of a number of atmospheric species of biological significance, including oxygen, ozone, carbon monoxide, formaldehyde, and hydrogen cyanide. Using a photochemical model of the early atmosphere, the chemical productionof these species over a wide range of atmospheric parameters were investigated. These calculations indicate that early atmospheric levels of O3 were significantly below the levels needed to provide UV shielding. The fate of volcanically emitted sulfur species, e.g., sulfur dioxide and hydrogen sulfide, was investigated in the early atmosphere to assess their UV shielding properties. The photochemical calculations show that these species were of insufficient levels, due in part to their short photochemical lifetimes, to provide UV shielding.

Levine, J. S.↗