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At least 73 records · Page 4

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NASA NTRS1974

The photodetachment cross-section and threshold energy of negative ions in carbon dioxide

Threshold energy and sunlight photodetachment measurements on negative carbon dioxide ions, using a 2.5 kw light pressure xenon lamp, show that: (1) Electron affinity of CO3(+) is larger than 2.7 e.V. and that an isomeric form of CO3(+) is likely an error; (2) The photodetachment cross section of CO3(-) will roughly be like a step function across the range of 4250 to 2500A, having its threshold energy at 4250A; (3) Sunlight photodetachment rate for CO3(-) is probably much smaller than elsewhere reported; and (4) The probability of having photodetached electrons re-attach to form negative ions is less than 1%. Mass identifying drift tube tests confirm that the slower ion is CO3(-), formed through the O(-) + 2CO2 yields CO3(-) + CO2 reaction.

Helmy, E. M.↗

NASA NTRS1974

Holographic recording materials development

Developments in the area of organic cis-trans isomerization systems for holographic memory applications are reported. The chemical research effort consisted of photochemical studies leading to the selection of a stilbene derivative and a polymer matrix system which have greatly improved refractive index differences between the cis and trans isomers as well as demonstrated efficiency of the photoisomerization process. In work on lithium niobate effects of sample stoichiometry and of read and write beam polarizations on recording efficiency were investigated. LiNbO3 was used for a study of angular sensitivity and of capability for simultaneous recording of extended objects without interference. The current status of LiNbO3 as a holographic recording material is summarized.

Source record↗

NASA NTRS1973

Botryococcene - A tetramethylated acyclic triterpenoid of algal origin

The green alga Botryococcus braunii, implicated in the formation of certain geological deposits, produces unusual isomeric C34H58 alkenes, botryococcene and isobotryococcene, during a particular physiological state. A structure for botryococcene is suggested, taking into account NMR techniques, oxidative degradation, and established biosynthetic principles. Botryococcene appears terpenoid in origin.

Cox, R. E.↗

NASA NTRS1974

Dicarboxylic acids in the Murchison meteorite

A large suite of aliphatic dicarboxylic acids was found in extracts from the carbonaceous chondrite. This suite includes many of the branched and straight chained isomers with up to nine carbon atoms. The large number of compounds and the isomeric distribution suggest that the acids are the product of an abiotic synthesis. The dicarboxylic acids found have been identified by their gas chromatography retention values and by comparison of their mass spectra with those of authentic standards.

Lawless, J. G.↗

NASA NTRS1975

Annealing of aromatic polyimide precursors

A study has been made of the thermal behavior of polyimide precursors: an isomeric pair of crystals of the complex formed by p-phenylenediamine with the separated isomers of the di-isopropyl ester of pyromellitic acid. Specimens of this material were isothermally annealed in the temperature range 120 C to 170 C for periods of time up to 1 week. Although this temperature range is well below that customarily used for imidizations, the working hypothesis was that it would be more likely that a polymer embodying at least part of the precursor structure could be formed if the molecular motion was minimized to that actually required for the formation of the imide linkage. The progress of the annealing was followed by: infrared spectroscopy, differential thermal analysis, powder X-ray diffraction, and thermal gravimetric analysis. Single crystal X-ray analysis of the meta monomer yields a structure of chains of alternating acid and base and suggests that this monomer is amenable to polymerization with a minimum of geometrical disruption.

Wakelyn, N. T.↗

NASA NTRS1975

Feasibility of Mossbauer survey meter for hydrocarbon and mineral reserves

The feasibility of developing a Mossbauer survey meter for geophysical prospecting was investigated. Various critical requirements that will have to be met by the source and absorber crystals in such an instrument were identified. It was concluded that a survey meter based on (Rh-103 resonance (40 kev) yields Rh-103) isomeric transition is feasible and should be developed.

Singh, J. J.↗

NASA NTRS1975

Molecular weight: Property relationships of high performance polymers used for adhesives and composites

Degradation of high performance polyimide precursor resins was investigated by measuring the molecular weight of the polymers in solution, using a membrane osmometer. It was found that polyimide precursor resins composed of BTDA and ODPA combined with DABP and MDA were unstable in DMAC. The degradation rate was found to depend upon the chemical nature of the isomeric diamine and the geometric structure about the amide linkage. The polymers of DABP were less susceptible to degradation than those of MDA and p,p'-compounds were more stable than m,m'-compounds. These results suggest that degradation is correlated with the basicity of the diamine. That is, the rate of the degradation reaction increases with the basicity of the diamine group in the polyimide precursor resin. The presence of water and a higher temperature increased the degradation rate of the polymers.

Kranbuehl, D.↗

NASA NTRS1976

Photoionization and ion cyclotron resonance studies of the ion chemistry of ethylene oxide

The formation of the ethylene oxide molecular ion and its subsequent ion-molecule reactions leading to the products C2H5O(+) and C3H5O(+) have been studied using time-resolved photoionization mass spectroscopy, ion cyclotron resonance spectroscopy, and photoelectron spectroscopy. An examination of the effects of internal energy on reactivity shows that the ratio of C3H5O(+) to C2H5O(+) increases by an order of magnitude with a single quantum of vibrational energy. The formation of (C2H4O/+/)-asterisk in a collision-induced isomerization is found which yields a ring-opened structure by C-C bond cleavage. The relaxed ring-opened C2H4O(+) ion reacts with neutral ethylene oxide by CH2(+) transfer to yield an intermediate product ion C3H6O(+) which gives C3H5O(+) by loss of H.

Corderman, R. R.↗

NASA NTRS1978

Isoprenoid hydrocarbons produced by thermal alteration of Nostoc muscorum and Rhodopseudomonas spheroides

The potential of algae and photosynthetic bacteria to serve as precursors of kerogen was studied to determine what factors affect the relative rates of formation of precursor hydrocarbons. Cells of Nostoc muscorum and Rhodopseudomonas spheroides were subjected to thermal alteration (by heating samples in glass tubes sealed under nitrogen) for two, four, and twelve weeks. Both unextracted and extracted cells in the absence and presence of montmorillonite were investigated, and the isoprenoid hydrocarbons produced in these experiments were determined. Phytane and five isomeric phytenes were the main hydrocarbons observed; their relative rates of formation in the different experimental conditions are described. No phytadienes, pristane, or pristenes were detected.

Philp, R. P.↗

NASA NTRS1978

Candidate interstellar molecules formed from ion-molecule reactions of NO

Molecular orbital calculations using the MINDO/3 method were performed on a series of small molecules to explore reactions of NO which could lead to formation of interstellar molecules. Specifically, equilibrium geometries, isomeric energies, heats of reactions, and reaction pathways were calculated for plausible ion-molecule reactions involving NO and NO(+). The results of these calculations suggest that HNO(+) and HON(+) could be present in observable abundance in interstellar clouds. These species can be formed by the reaction of NO with H3(+) but not by NO(+) with H2. Moreover, they are stable to dissociation and do not react with H2 to re-form NO or to form isomers of HNOH(+).

Loew, G. H.↗

NASA NTRS1978

Field ionization kinetic and electron impact studies of gas phase transition states - The cyclic bromonium ion

Cis- and trans-isomers of 4-t-butylcyclohexyl bromide were studied to determine the mechanism of cyclic bromonium ion formation. The field ionization kinetic and electron impact data indicate that the formation of the cyclic structure occurs simultaneously with loss of the neutral fragment. The data also show that little or no gas-phase cis-trans isomerization occurs.

Green, M. M.↗

NASA NTRS1978

Methods for the photochemical utilization of solar energy

The paper considers the 'ground rules' which govern the efficiency of photochemical solar energy conversion and then summarizes the most promising approaches in each of three categories: photochemically assisted thermal systems for the heating and/or cooling of structures; photogalvanic systems for the production of electrical power in applications, such as photorechargeable batteries or inexpensive 'solar cells'; and photochemical formation of fuels for combustion and for use as chemical feedstocks or foods. Three concepts for the photochemical utilization of solar energy in space are found to be particularly promising: (1) photochemical trans-cis isomerization of indigold dyes for photoassisted heating or cooling, (2) the redox stabilized photoelectrolysis cell for the production of hydrogen (and/or oxygen or other useful chemicals), and (3) the liquid-junction photovoltaic cell for the production of electrical power.

Schwerzel, R. E.↗

NASA NTRS1978

Mass spectrometry

A review of mass spectrometry in organic chemistry is given, dealing with advances in instrumentation and computer techniques, selected topics in gas-phase ion chemistry, and applications in such fields as biomedicine, natural-product studies, and environmental pollution analysis. Innovative techniques and instrumentation are discussed, along with chromatographic-mass spectrometric on-line computer techniques, mass spectral interpretation and management techniques, and such topics in gas-phase ion chemistry as electron-impact ionization and decomposition, photoionization, field ionization and desorption, high-pressure mass spectrometry, ion cyclotron resonance, and isomerization reactions of organic ions. Applications of mass spectrometry are examined with respect to bio-oligomers and their constituents, biomedically important substances, microbiology, environmental organic analysis, and organic geochemistry.

Burlingame, A. L.↗

NASA NTRS1980

Photochemistry of monodentate and bidentate carbonato complexes of rhodium (3)

A scheme for the photochemical fixation of water is proposed which involves a five-step reaction sequence; the first step involves the 2 electron reduction of a metal by a coordinated carbonate ligand, with corresponding oxidation of the carbonate to CO2 and O2. Ligand field photolysis of trans- (RH(en)2 H2O CO3) ClO4, and (Rh(en)2 CO3) CLO4 have been studied in the solid state and in aqueous solution at various pH values. Both salts are photoinert in the solid phase, but are quite photoreactive in aqueous solution. In solution, the monodentate ion undergoes efficient isomerization to a mixture of cis and trans - (Rh(en)2 H2O CO3)+, presumably with water exchange. A minor pH increase upon photolysis is evidence of inefficient carbonate (CO3 =) release, with formation of (Rh(en)2 (H2O)2)3+. In contrast, aqueous solutions of the bidentate carbonato complex undergo efficient pH decrease upon ligand field photolysis. Changes in the electronic spectrum (200-500 nm) and pH changes indicate that the desired redox is occurring. The pH increase is due to the aqueous behavior of CO2.

Sheridan, P. S.↗

NASA NTRS1981

Characterization of initial cure reactions in propargyl and nadic end capped model compounds

Imide model compounds containing propargyl and nadic groups were studied to obtain a fundamental understanding of the reaction of these groups attached to imide oligomers. The initial cure reactions were examined by a variety of characterization techniques including high pressure liquid chromatography, infrared spectroscopy, thermal analyses, and mass spectroscopy. The initial step in the cure of propargyl end capped model compounds probably involved the formation of a new terminal acetylenic group. Configurational changes involving endo/exo isomerism was found in the nadimide model compounds. Nadimide compounds heated in air and in nitrogen appeared to cure by different mechanisms.

Young, P. R.↗

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 NTRS1980

Chemical analysis of LARC-160 polyimide

As part of a detailed NASA-sponsored study of chemical composition/property sensitivity of the LARC-160 polymerization of monomeric reactants (PMR) polyimide system, a number of liquid chromatographic techniques have been employed. The ester monomers in this system are characterized by a reverse-phase ion-suppression method. Mono, di, and triesters of the 3,3',4,4'-benzophenonetetracarboxylic acid ingredient are identified and their isomeric forms resolved. The 5-norbornene-2,3-dicarboxylic acid ester (nadic ester) endcapper is detected by low wavelength ultraviolet sensing. A second method, reverse-phase ion-pair chromatography, is employed for determining unreacted amines. The extent of resin B-staging is monitored through analysis of the ester/amine oligomers.

Dynes, P. J.↗

NASA NTRS1982

Recent advances in the chemical modification of unsaturated polymers

The present discussion has the objective to update the most comprehensive reviews on the considered subject and to fill in the gaps of less complete, but more modern treatments. Only simple chemical functionalization or structural modification of unsaturated polymers are covered, and the literature of diene polymer modification since 1974 is emphasized. Attention is given to hydrogenation, halogenation and hydrohalogenation, cyclization, cis-trans isomerization, epoxidation, ene and other cycloaddition reactions, sulfonation, carboxylation, phosphonylation, sulfenyl chloride addition, carbene addition, metalation, and silylation. It is pointed out that modern synthetic reagents and catalysts have been advantageously employed to improve process and/or product quality. Synthetic techniques have been refined to allow the selective modification of specific polymer microstructures or blocks.

Schulz, D. N.↗