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At least 163 records · Page 9

Aliphatic hydrocarbons of the Murchison meteorite

Hydrocarbon fractions from the Murchison meteorite were prepared using benzene-methanol as the extraction solvent, fractionated on silica gel columns, and analyzed using gas chromatography combined with mass spectrometry and IR and NMR techniques. Results indicate that the most abundant aliphatic hydrocarbon components of the Murchison meteorite are C15 to C30 branched-alkyl-substituted mono-, di-, and tricyclic alkanes. It is shown that the n-alkanes, methyl alkanes, and isoprenoid alkanes that are sometimes found in extracts of the Murchison meteorite are terrestrial contaminants.

Cronin, John R.↗

Polymeric routes to silicon carbide and silicon oxycarbide CMC

An overview of two approaches to the formation of ceramic composite matrices from polymeric precursors is presented. Copolymerization of alkyl- and alkenylsilanes (RSiH3) represents a new precursor system for the production of Beta-SiC on pyrolysis, with copolymer composition controlling polymer structure, char yield, and ceramic stoichiometry and morphology. Polysilsesquioxanes which are synthesized readily and can be handled in air serve as precursors to Si-C-O ceramics. Copolymers of phenyl and methyl silsesquioxanes display rheological properties favorable for composite fabrication; these can be tailored by control of pH, water/methoxy ratio and copolymer composition. Composites obtained from these utilize a carbon coated, eight harness satin weave Nicalon cloth reinforcement. The material exhibits nonlinear stress-strain behavior in tension.

Hurwitz, Frances I.↗

An assessment of potential degradation products in the gas-phase reactions of alternative fluorocarbons in the troposphere

Tropospheric chemical transformations of alternative hydrofluorocarbons (HCF's) and hydrochlorofluorocarbons (HCFC's) are governed by hydroxyl radical initiated oxidation processes, which are likely to be analogous to those known for alkanes and chloroalkanes. A schematic diagram is used to illustrate plausible reaction mechanisms for their atmospheric degradation, where R, R', and R'' denote the F- and/or Cl-substituted alkyl groups derived from HCF's and HCFC's subsequent th the initial H atom abstraction by HO radicals. At present, virtually no kinetic data exist for the majority of these reactions, particularly for those involving RO. Potential degradation intermediates and final products include a large variety of fluorine- and/or chlorine-containing carbonyls, acids, peroxy acids, alcohols, hydrogen peroxides, nitrates and peroxy nitrates, as summarized in the attached table. Probably atmospheric lifetimes of these compounds were also estimated. For some carbonyl and nitrate products shown in this table, there seem to be no significant gas-phase removal mechanisms. Further chemical kinetics and photochemical data are needed to quantitatively assess the atmospheric fate of HCF's and HCFC's, and of the degradation products postulated in this report.

Niki, Hiromi↗

Boron-carbon-silicon polymers and ceramic and a process for the production thereof

The present invention relates to a process for the production of an organoborosilicon preceramic polymer of the structure: wherein R 1 is selected from alkyl having from 1 to 10 carbon atoms or phenyl, and x is selected from 0, 1, 2 or 3; which is pyrolyzable to produce a refractory material comprising inorganic compounds of Si, C and B, which process comprises: contacting a silicon containing compound of the structure: (R 1 ) x --Si--(CH=CH 2 ) 4- x or (R 1 ) x Si--(C=CH) 4- x with a boron containing compound selected from H 3 B:BH 3 , H 3 B:NH 3 , BH 3 :N(R 2 ) 3 wherein R 2 is selected from methyl, ethyl, propyl, butyl or phenyl in an inert atmosphere at a temperature of between about 90° and 170° C. for between about 0.1 and 20 hr and recovering the prepolymer. The prepolymer is pyrolyzed to produce a ceramic article useful in high temperature (e.g., aerospace) or extreme environmental applications.

Salvatore Riccitiello↗

Substituted 1,1,1-triaryl 2,2,2-trifluoroethanes and processes for their synthesis

Synthetic procedures to tetraalkyls, tetraacids, and dianhydrides substituted 1,1,1-triaryl 2,2,2-trifluoroethanes which comprises: (1) 1,1-bis(dialkylaryl) 1-aryl-2,2,2-trifluoroethane, (2) 1,1-bis(dicarboxyaryl) 1-aryl-2,2,2-trifluoroethane, or (3) cyclic dianhydride or diamine of 1,1-bis(dialkylaryl) 1-aryl-2,2,2-trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or alkyl substituted or disubstituted anilines. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Alston, William B.↗

Relationship of peroxyacetyl nitrate to active and total odd nitrogen at northern high latitudes - Influence of reservoir species on NO(x) and O3

The partitioning of relative nitrogen in the Arctic and the sub-Arctic troposphere based on measurements conducted during the 1988 Arctic Boundary Layer Expedition (ABLE 3A) is described. The first set of comprehensive odd nitrogen and O3 measurements from the Arctic/sub-Arctic free troposphere shows that a highly aged air mass that has persisted under very cold conditions is present. A large fraction of the odd nitrogen appears to be present in the form of reservoir species such as PAN. Significant quantities of as yet unknown reactive nitrogen species, such as complex alkyl nitrates and pernitrates, are expected to be present. Together with PAN, these nitrate and pernitrate reservoir species could control the entire NO(x) availability of the high-latitude troposphere and in turn influence the O3 photochemistry of the region. The role of PAN in influencing the O3 reservoir is shown to be important and may be responsible for the increasing O3 temporal trend observed at high latitudes.

Singh, H. B.↗

Structure and energetics of model amphiphilic molecules at the water liquid-vapor interface - A molecular dynamics study

A molecular dynamics study of adsorption of p-n-pentylphenol at infinite dilution at the water liquid-vapor interface is reported. The calculated free energy of adsorption is -8.8 +/- 0.7 kcal/mol, in good agreement with the experimental value of -7.3 kcal/mol. The transition between the interfacial region and the bulk solution is sharp and well-defined by energetic, conformational, and orientational criteria. At the water surface, the phenol head group is mostly immersed in aqueous solvent. The most frequent orientation of the hydrocarbon tail is parallel to the interface, due to dispersion interactions with the water surface. This arrangement of the phenol ring and the alkyl chain requires that the chain exhibits a kink. As the polar head group is being moved into the solvent, the chain length increases and the tail becomes increasingly aligned toward the surface normal, such that the nonpolar part of the molecule exposed to water is minimized. The same effect was achieved when phenol was replaced by a more polar head group, phenolate.

Pohorille, Andrew↗

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

PAHs are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites, are identified, with a net abundance of about 0.0001 g/g (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins.

Sagan, Carl↗

Hydrocarbon and nonhydrocarbon derivatives of cyclopropane

The methods used to prepare and purify 19 hydrocarbon derivatives of cyclopropane are discussed. Of these hydrocarbons, 13 were synthesized for the first time. In addition to the hydrocarbons, six cyclopropylcarbinols, five alkyl cyclopropyl ketones, three cyclopropyl chlorides, and one cyclopropanedicarboxylate were prepared as synthesis intermediates. The melting points, boiling points, refractive indices, densities, and, in some instances, heats of combustion of both the hydrocarbon and nonhydrocarbon derivatives of cyclopropane were determined. These data and the infrared spectrum of each of the 34 cyclopropane compounds are presented in this report. The infrared absorption bands characteristic of the cyclopropyl ring are discussed, and some observations are made on the contribution of the cyclopropyl ring to the molecular refractions of cyclopropane compounds.

Slabey, Vernon A↗

A reexamination of amino acids in lunar soil

Amino acids in lunar soils provide an important indicator of the level of prebiotic organic compounds on the moon. The results provide insight into the chemistry of amino acid precursors, and furthermore, given the flux of carbonaceous material to the moon, we can evaluate the survival of organics upon impact. The amino acid contents of both hydrolyzed and unhydrolyzed hot-water extracts of Apollo 17 lunar soil were determined using ophthaldialdehyde/N-acetyl cysteine (OPA/NAC) derivatization followed by HPLC analysis. Previous studies of lunar amino acids were inconclusive, as the technique used (derivatization with ninhydrin followed by HPLC analysis) was unable to discriminate between cosmogenic amino acids and terrestrial contaminants. Cosmogenic amino acids are racemic, and many of the amino acids found in carbonaceous meteorites such as Murchison, i.e., alpha-amino-i-butyric acid (aib), are extremely rare on Earth. The ninhydrin method does not distinguish amino acid enantiomers, nor does it detect alpha-alkyl amino acids such as aib, whereas the OPA/NAC technique does both.

Brinton, K. L. F.↗

Highly fluorinated polymers

The topics covered include the following: highly fluorinated polyesters; N-alkylated polyamides; highly fluorinated polyethers; and silicon-containing fluoropolymers.

Cassidy, Patrick E.↗

Trifluoromethyl-substituted polymers

Current work sponsored by the grant at Southwest Texas State University is directed toward the synthesis and characterization of: (1) N-alkylated polyamides derived from o-fluorinated diacids; (2) highly fluorinated polyethers; (3) polyesters derived from 2-hydroxy-2-propyl substituted arenes and/or 2,5-difluoroterephthalic acid; and (4) silicon-containing fluoropolymers. Work during the period from 1 July to 31 Dec. 1993 focused primarily on items 3 and 4 and on the development of a phosphorus containing modification of '12F-PEK.'

Source record↗

Peroxy radical measurements with NCAR's chemical amplifier

The present NCAR instrument for HO2/RO2 measurements has been described previously. It is based on the reactions involving HO2, RO2, and HO radicals with CO and NO. Since (HO2) + (RO2) + (HO) is much greater than (HO) for most atmospheres, it is useful as a peroxy radical detector. Operation of the instrument depends on the creation of a chemical chain reaction which is initiated as HO2 and RO2 radicals in ambient air encounter added NO gas; this forms an NO2 molecule and an HO or RO radical: HO2(RO2) + NO yields HO(RO) + NO2. RO radicals react relatively efficiently with O2 to form an HO2 radical, and subsequently an HO-radical, by reaction with NO. CO gas added to the reaction chamber during part of the operating cycle, recycles the HO to HO2; HO + CO (+O2) yields HO2 + CO2. The reaction sequence may form several hundred NO2 molecules per HO2 (RO2) originally present, before chain termination occurs. The added CO is replaced by N2 addition periodically so that the chain reaction is suppressed, and a 'blank' signal resulting from NO2, O3 and possibly other NO2-forming species (non-chain processes) in ambient air is recorded. The difference between the signal with and without CO is proportional to the peroxy radical concentration. The NO2 produced is monitored using a sensitive luminol chemiluminescence detector system. In the NCAR instrument the length of the amplification chain is determined using a stable source of HO2 radicals (H2O2 thermal decomposition); the ratio of the signal seen with CO present to that with N2 present gives the sensitivity of the instrument to HO2 (molecules of NO2 formed/peroxy radical). The instrument is automated to carry out in hourly repeated cycles: (1) chain length determination; (2) NO2 calibration; and (3) linearity check on the response of signals. One minute averages of signals are normally recorded. The sensitivity of the instrument to detect peroxy radicals is in the pptv range. The present instrument has operated continuously (24 hr/day) in the field studies which extended over a period of several weeks. The major advantages of this instrument are as follows: (1) its relative simplicity; (2) low power requirements; and (3) its rapid response to all types of peroxy radicals--HO2, CH3O2 and the higher alkyl and acyl peroxy radicals; however not all RO2 species generate HO2 radicals with perfect efficiency and hence have somewhat lower response/molecule than HO2 radicals.

Cantrell, Christopher↗

Comprehensive investigation of HgCdTe metalorganic chemical vapor deposition

The principal objective of this experimental and theoretical research program was to explore the possibility of depositing high quality epitaxial CdTe and HgCdTe at very low pressures through metalorganic chemical vapor deposition (MOCVD). We explored two important aspects of this potential process: (1) the interaction of molecular flow transport and deposition in an MOCVD reactor with a commercial configuration, and (2) the kinetics of metal alkyl source gas adsorption, decomposition and desorption from the growing film surface using ultra high vacuum surface science reaction techniques. To explore the transport-reaction issue, we have developed a reaction engineering analysis of a multiple wafer-in-tube ultrahigh vacuum chemical vapor deposition (UHV/CVD) reactor which allows an estimate of wafer or substrate throughput for a reactor of fixed geometry and a given deposition chemistry with specified film thickness uniformity constraints. The model employs a description of ballistic transport and reaction based on the pseudo-steady approximation to the Boltzmann equation in the limit of pure molecular flow. The model representation takes the form of an integral equation for the flux of each reactant or intermediate species to the wafer surfaces. Expressions for the reactive sticking coefficients (RSC) for each species must be incorporated in the term which represents reemission from a wafer surface. The interactions of MOCVD precursors with Si and CdTe were investigated using temperature programmed desorption (TPD) in ultra high vacuum combined with Auger electron spectroscopy (AES). These studies revealed that diethyltellurium (DETe) and dimethylcadmium (DMCd) adsorb weakly on clean Si(100) and desorb upon heating without decomposing. These precursors adsorb both weakly and strongly on CdTe(111)A, with DMCd exhibiting the stronger interaction with the surface than DETe.

Raupp, Gregory B.↗

Aldehydes in hydrothermal solution - Standard partial molal thermodynamic properties and relative stabilities at high temperatures and pressures

Aldehydes are common in a variety of geologic environments and are derived from a number of sources, both natural and anthropogenic. Experimental data for aqueous aldehydes were taken from the literature and used, along with parameters for the revised Helgeson-Kirkham-Flowers (HKF) equations of state, to estimate standard partial molal thermodynamic data for aqueous straight-chain alkyl aldehydes at high temperatures and pressures. Examples of calculations involving aldehydes in geological environments are given, and the stability of aldehydes relative to carboxylic acids is evaluated. These calculations indicate that aldehydes may be intermediates in the formation of carboxylic acids from hydrocarbons in sedimentary basin brines and hydrothermal systems like they are in the atmosphere. The data and parameters summarized here allow evaluation of the role of aldehydes in the formation of prebiotic precursors, such as amino acids and hydroxy acids on the early Earth and in carbonaceous chondrite parent bodies.

Schulte, Mitchell D.↗

Substituted 1,1,1-triaryl-2,2,2-trifluoroethanes and processes for their synthesis

Synthetic procedures are given for tetraalkyl, tetraacid and dianhydrides substituted 1,1,1-triaryl-2,2,2-trifluoroethanes which comprises: (1) 1,1-bis (dialkylaryl) 1-aryl-2,2,2 trifluoroethane; (2) 1,1-bis (dicarboxyaryl) 1-aryl-2,2,2 trifluoroethane; or (3) cyclic dianhydride or diamine of 1,1-bis (dialkylaryl) 1-aryl-2,2,2 trifluoroethanes. The synthesis of (1) is accomplished by the condensation reaction of an aryltrifluoromethyl ketone with a dialkylaryl compound. The synthesis of (2) is accomplished by oxidation of (1). The synthesis dianhydride of (3) is accomplished by the conversion of (2) to its corresponding cyclic dianhydride. The synthesis of the diamine is accomplished by the similar reaction of an aryltrifluoromethyl ketone with aniline or alkyl substituted or disubstituted anilines. Also, other derivatives of the above are formed by nucleophilic displacement reactions.

Alston, William B.↗

Hypervelocity impact survivability experiments for carbonaceous impactors, part 2

Hypervelocity impact experiments were performed to further test the survivability of carbonaceous impactors and to determine potential products that may have been synthesized during impact. Diamonds were launched by the Ames two-stage light gas gun into Al plate at velocities of 2.75 and 3.1 km sec(exp -1). FESEM imagery confirms that diamond fragments survived in both experiments. Earlier experiments found that diamonds were destroyed on impact above 4.3 km sec(exp -1). Thus, the upper stability limit for diamond on impact into Al, as determined from our experimental conditions, is between 3.1 and 4.3 km sec(exp -1). Particles of the carbonaceous chondrite Nogoya were also launched into Al at a velocity of 6.2 km sec (exp -1). Laser desorption (L (exp 2) MS) analyses of the impactor residues indicate that the lowest and highest mass polycyclic aromatic hydrocarbons (PAH's) were largely destroyed on impact; those of intermediate mass (202-220 amu) remained at the same level or increased in abundance. In addition, alkyl-substituted homologs of the most abundant pre-impacted PAH's were synthesized during impact. These results suggest that an unknown fraction of some organic compounds can survive low to moderate impact velocities and that synthesized products can be expected to form up to velocities of, at least, 6.5 km sec(exp -1). We also present examples of craters formed by a unique microparticle accelerator that could launch micron-sized particles of almost any coherent material at velocities up to approximately 15 km sec(exp -1). Many of the experiments have a direct bearing on the interpretation of LDEF craters.

Bunch, T. E.↗

Double layer hydroxide minerals as host structures for bioorganic molecules

A central problem in molecular evolution concerns the selective concentration from dilute, multicomponent solution of source molecules into a reactive environment, where formation of larger molecular assemblages can take place. Minerals consisting of positively charged, separable metal hydroxide sheets have proven capable of these functions. This common structural type is represented by minerals such as pyroaurite (Mg-Fe(3+) hydroxide), hydrotalcite (Mg-Al), green rust Fe(2+)-Fe(3+) and others. Effective interlayer sorption is demonstrated for orthophosphate and condensed phosphates, anionic alkyl compounds, polypeptides, nucleic acids, cyanide complexes and glycolaldehyde phosphate, the latter shown to readily oligomerize to form and selectively retain racemic hexose -2, 4, 6-phosphates, preferentially of altrose (Pitsch, et al, 1993). The selective aldomerization and retention effects correlate with the charge distribution in the host mineral structure and the stereochemistry of the substrate molecules. Interaction between nucleic acid bases, and between the cyanide groups of glycolaldehyde phosphate nitrile at the low water activity in the mineral interlayer is indicated by doubling of the monomeric separation of the hydroxide mineral sheets.

Lee, Ton↗