Diimide formation via an aziridine rearrangement.
Gas evolution in preparation of N-t- butylaziridine-2-carboxylic acid hydrazide by standard procedures explained by diimide formation
Clough, S. C.↗
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Organic contamination analysis: High resolution mass spectrometric analysis of surface organics on selected areas of Surveyor 3
The mirror and middle shroud were extracted for organics by washing the surfaces with solvents. The techniques are discussed. Ion microprobe analyses of the primarily atomic species are presented. The sources of the organic contaminants are: (1) hydrocarbons from lubricating oils and general terrestrial contamination, (2) dioctyl phthalate, probably from polyethylene bagging material (the plasticizer), (3) carboxylic acids from decomposition of grease and general terrestrial contamination, (4) silicones from sources such as lubricating oil, (5) outgassing of electronics and plasticizer, (6) vinyl alcohol and styrene copolymer, probably from electronic insulation, and (7) nitrogenous compounds from the lunar module and possibly Surveyor 3 engine exhaust.
Simoneit, B. R.↗
Polyimide foam for the thermal insulation and fire protection
The preparation of chemically resistant and flame retardant foams from polyfunctional aromatic carboxylic acid derivatives and organic polyisocyanates is outlined. It was found that polyimide foams of reproducible density above 1 lb./ft. and below 6 lbs./cu ft. can be obtained by employing in the reaction of least 2% by weight of siloxane-glycol copolymer as a surfactant which acts as a specific density control agent. Polyimide foams into which reinforcing fibers such as silicon dioxide and carbon fibers may be incorporated were also produced.
Rosser, R. W.↗
Study of the organic matter in the DSDP /JOIDES/ cores, legs 10-15
The composition of the organic matter collected on legs 10 to 15 of the DSDP (Deep Sea Drilling Project) is described. Distributions of various alkanes, carboxylic acids, steroids and terpenoids, isoprenoid ketones and olefins, and aromatic polycyclic compounds are given. Samples analyzed had terrigenous clay components, with variable organic carbon contents and thus diverse solvent soluble matter. The distribution patterns for the various compound series monitored were of marine derivation, with the terrigenous components superimposed. Diagenesis of steroids appeared to proceed via both stanones and stanols to their respective steranes. Degradative processes were observed to be operative: oxidative products, mainly ketones derived from steroids and phytol, were identified, probably due to microbial alteration prior to or during sedimentation. Loss of alkane and fatty acid C preferences and presence of polycyclic aromatics evinced maturation. Results indicate that the accumulation, degradation, diagenesis and maturation of organic matter occurs in various steps in the deep sea environment.
Simoneit, B. R. T.↗
Collection and analysis of organic gases from natural ecosystems - Application to poultry manure
Combined gas chromatography-mass spectrometry was used to identify volatile compounds generated from chicken manure and collected in Poropak QS-Carbosieve B traps. Various alcohols, ketones, esters, and carboxylic acids together with dimethyl sulfide and dimethyl disulfide were detected when the wastes were incubated in an argon atmosphere. Significant amounts of dimethyl sulfide and dimethyl disulfide but few other compounds were found when the manure was incubated in air
Smith, M. S.↗
Organic matter in eolian dusts over the Atlantic Ocean
The elemental and mineralogical composition and the microfossil and detritus content of particulate fallout from the lower troposphere over the Atlantic Ocean have been extensively documented in earlier work, and it was possible to ascribe terrigenous source areas to such fallout. A brief review of the organic geochemistry of eolian dusts is also presented here. The lipids of eolian dusts sampled from the air mass over the eastern Atlantic from about 35 deg N to 30 deg S were analyzed here. These lipids consisted mainly of normal alkanes, carboxylic acids and alcohols. The n-alkanes were found to range from n-C23 to n-C35 with high CPI values and maximizing at n-C27 in the North Atlantic, at n-C29 in the equatorial Atlantic and at n-C31 in the South Atlantic. The n-fatty acids had mostly bimodal distributions, ranging from n-C12 to n-C30 (high CPI), with maxima at n-C16 and in the northern samples at n-C24 and in the southern samples at n-C26. The n-alcohols ranged from n-C12 to n-C32, with high CPI values and maxima mainly at n-C28. The compositions of these lipids indicated that their terrigenous sources were comprised mainly of higher plant vegetation and desiccated lacustrine mud flats on the African continent.
Simoneit, B. R. T.↗
Structural studies on HCN oligomers
NMR spectral studies on the HCN oligomers suggest the presence of carboxamide and urea groupings. The release of CO2, H2O, HCN, CH3CN, HCONH2 and pyridine on pyrolysis is consistent with the presence of these groupings as well as carboxylic acid groups. No basic primary amine groupings could be detected with fluorescamine. Hydrazinolysis of the HCN oligomers releases 10% of the amino acids normally released by acid hydrolysis. The oligomers give a positive biuret test but this is not due to the presence of peptide bonds. There is no conclusive evidence for the presence of peptide bonds in the HCN oligomers. No diglycine was detected on partial hydrolysis of the HCN oligomers at pH 8.5 suggesting that HCN oligomers were not a source of prebiotic peptides.
Ferris, J. P.↗
Advanced inorganic separators for alkaline batteries
A flexible, porous battery separator comprising a coating applied to a porous, flexible substrate is described. The coating comprises: (1) a thermoplastic rubber-based resin which is insoluble and unreactive in the alkaline electrolyte; (2) a polar organic plasticizer which is reactive with the alkaline electrolyte to produce a reaction product which contains a hydroxyl group and/or a carboxylic acid group; and (3) a mixture of polar particulate filler materials which are unreactive with the electrolyte, the mixture comprising at least one first filler material having a surface area of greater than 25 meters sq/gram, at least one second filler material having a surface area of 10 to 25 sq meters/gram, wherein the volume of the mixture of filler materials is less than 45% of the total volume of the fillers and the binder, the filler surface area per gram of binder is about 20 to 60 sq meters/gram, and the amount of plasticizer is sufficient to coat each filler particle. A method of forming the battery separator is also described.
Sheibley, D. W.↗
Advanced inorganic separators for alkaline batteries and method of making the same
A flexible, porous battery separator includes a coating applied to a porous, flexible substrate. The coating comprises: (1) a thermoplastic rubber-based resin which is insoluble and unreactive in the alkaline electrolyte, (2) a polar organic plasticizer which is reactive with the alkaline electrolyte to produce a reaction product which contains a hydroxyl group and/or a carboxylic acid group, and (3) a mixture of polar particulate filler materials which are unreactive with the electrode. The mixture comprises at least one first filler material having a surface area of greater than 25 sq meters/gram, at last one second filler material having a surface area of 10 to 25 sq meters/gram. The volume of the mixture of filler materials is less than 45% of the total volume of the fillers and the binder. The filler surface area per gram of binder is about 20 to 60 sq meters/gram, and the amount of plasticizer is sufficient to coat each filler particle.
Sheibley, D. W.↗
Participation of Ethylene in Two Modes of Gravistimulation of Shoots
In order to elucidate the role of ehtylene in gravitropism, detailed time courses for ethylene production in horizontal and upright plants were measured. Tomato and pea were chosen as examples of plants which exhibit different patterns of gravitropic curvature. Tomato seedlings were placed in gas-tight lucite boxes from which air was sampled and analyzed for ethylene. During the first 2 min interval after one set of plants was turned horizontal ethylene production was double the baseline. Similarly, plants rotated 3 rpm about a vertical axis transiently doubled ethylene production when the axis was shifted 90 deg. In order to clarify the role of this 2-min burst, the effect of exogenous ethylene was studied. In peas, epicotyls were excised, equilibrated until wound ethylene had subsided to a low stable level, and ethylene production was measured in vertical and horizontal segments. As for tomatoes, excised pea epicotyls increased their rate of ethylene production during the first 2 min of gravistimulation. Also, very low concentrations of exogenous ethylene slightly enhance curvature. On the other hand, higher levels of ethylene and 1-aminocyclopropane-1-carboxylic acid (ACC) inhibit overall curvature.
Harrison, M.↗
Increased gluconeogenesis in rats exposed to hyper-G stress
The effect of glucogenesis on the plasma glucose and liver glycogen of rats exposed to hyper-G stress is investigated. Twelve male Sprague-Dawley rats are injected with C-14 lactate, alanine, of glycerol, and six of the rats are exposed to 3.1 G for 0.25, 0.50, and 1.0 hr. The plasma glucose and liver glycogen of the centrifuged and noncentrifuged rats are analyzed. A significant increase in the C-14 incorporation of the substrate into the plasma glucose and liver glycogen is observed in the centrifuged rats. The injection of 5-methoxyindole-2-carboxylic acid, a gluconeogenesis inhibitor, results in a blocked increase in plasma glucose and liver glycogen. The role of epinephrine on the hyperglycemic and liver glycogen responses of centrifuged rats is studied. It is concluded that the initial increase in plasma glucose and liver glycogen in rats exposed to hyper-G stress is the result of an increased rate of gluconeogenesis.
Daligcon, B. C.↗
Increased gluconeogenesis in rats exposed to hyper-G stress
The effect of gluconeogenesis on the levels of plasma glucose and liver glycogen was studied in rats exposed to hyper-G stress. Incorporation of lactate, alanine, or glycerol, labeled with C-14, into plasma glucose and liver glycogen was measured in rats centrifuged at 3.1 G for 0.25, 0.50, and 1.0-hr periods, and was compared to noncentrifuged controls injected with appropriate glycogen precursors. It was found that exposure to G-stress leads to increased incorporation from all three substrates into both plasma glucose and liver glycogen. These early incorporation increases were blocked upon pre-G administration of 5-methoxyindole-2-carboxylic acid, a gluconeogenesis inhibitor, or propanolol, a beta-adrenergic blocker, as well as by adrenodemedullation. Results indicate that the rapid rise in plasma glucose, as well as in liver glycogen in rats exposed to hyper-G stress is due to an increased rate of gluconeogenesis, and that epinephrine, released in response to hyper-G-induced activation of the sympathetic-adrenal system, plays a dominant role during the early stages of hyper-G stress.
Daligcon, B. C.↗
Ion exchange polymers and method for making
An ion exchange polymer comprised of an alkali metal or alkaline earth metal salt of a poly(carboxylic acid) in a poly(vinyl acetal) matrix is described. The polymer is made by treating a mixture made of poly(vinyl alcohol) and poly(acrylic acid) with a suitable aldehyde and an acid catalyst to cause acetalization with some cross-linking. The material is then subjected to an alkaline aqueous solution of an alkali metal salt or an alkali earth metal salt. All of the film forming and cross-linking steps can be carried out simultaneously, if desired.
Philipp, Warren H.↗
Enhancement of perfluoropolyether boundary lubrication performance: I. Preliminary results
A ball bearing simulator operating under starved conditions was used to evaluate the boundary lubrication performance of a perfluoropolyether (PFPE) Krytox 143 AB. Several approaches to enhance boundary lubrication were studied. These included: (1) soluble boundary additives, (2) bearing surface modifications, (3) 'run-in' surface films, and (4) ceramic bearing components. In addition, results were compared with two non-perfluorinated liquid lubricant formulations. Based on these preliminary tests, the following tentative conclusions can be made: (1) substantial improvements in boundary lubrication performance were observed with a beta-diketone boundary additive and a tricresyl phosphate (TCP) liquid surface pretreatment; (2) the use of rough Si3N4 balls (Ra = 40 micro-in) also provided substantial improvement but with concomitant abrasive wear; (3) marginal improvements were seen with two boundary additives (a phosphine and a phosphatriazine) and a neat (100%) fluid (a carboxylic acid terminated PFPE); and surface pretreatments with a synthetic hydrocarbon, a PTFE coating, and TiC coated 440C and smooth Si3N4 balls (R(sub a) less than 1 micro-in); and (4) two non-PFPE lubricant formulations (a PAO and a synthetic hydrocarbon) yielded substantial improvements.
Jones, W. R., Jr.↗
Enhancement of Perfluoropolyether Boundary Lubrication Performance
A ball bearing simulator operating under starved conditions was used to perform screening tests to evaluate the boundary lubrication performance of a branched perfluoropolyether (PFPE), K-143 AB. Several approaches to enhance boundary lubrication were studied. These included: (1) soluble boundary additives, (2) bearing surface modifications, (3) 'run-in' surface films, and (4) ceramic bearing components. In addition, results were compared with two non-perfluorinated liquid lubricant formulations. Based on these tests, the following tentative conclusions can be made: (1) Substantial improvements in boundary lubrication performance were observed with a beta-diketone boundary additive and a tricresyl phosphate (TCP) liquid surface pretreatment, (2) the use of rough Si3N4 balls (R(sub a) = 40 micro-inch) also provided increases in test duration, but with concomitant abrasive wear, (3) moderate improvements were seen with two boundary additives (a phosphine and a phosphatriazine) and a neat (100%) fluid (a carboxylic acid terminated PFPE); and small improvements with surface pretreatments with synthetic hydrocarbons, a polytetrafluoroethylene (PTFE) coating, and TiC coated 440 C and smooth Si3N4 balls (R(sub a) = 1 micro-inch), and (4) two non-PFPE lubricant formulations (a polyalphaolefin (PAO) and synthetic hydrocarbon) yielded substantial improvements.
Jones, W. R., Jr.↗
Interaction of Light and Ethylene on Stem Gravitropism
The major objective of this study was to evaluate light-regulated ethylene production during gravitropic bending in etiolated pea stems. Previous investigations indicated that ethylene production increases after gravistimulation and is associated with the later (counter-reactive) phase of bending. Additionally, changes in the counter-reaction and locus of curvature during gravitropism are greatly influenced by red light and ethylene production. Ethylene production may be regulated by the levels of available precursor (1-aminocyclopropane-l-carboxylic acid, ACC) via its synthesis, conjugation to malonyl-ACC or glutamyl-ACC, or oxidation to ethylene. The regulation of ethylene production by quantifying ACC and conjugated ACC levels in gravistimulated pea stemswas examined. Also measured was the changes in protein and enzyme activity associated with gravitropic curvature by electrophoretic and spectrophotometric techniques. An image analysis system was used to visualize and quantify enzymatic activity and transcriptional products in gravistimulated and red-light treated etiolated pea stem tissues.
Harrison, Marcia A.↗
Chemical Constraints Governing the Origin of Metabolism: The Thermodynamic Landscape of Carbon Group Transformations
The thermodynamics of organic chemistry under mild aqueous conditions was examined in order to begin to understand its influence on the structure and operation of metabolism and its antecedents. Free energies were estimated for four types reactions of biochemical importance carbon-carbon bond cleavage and synthesis, hydrogen transfer between carbon groups, dehydration of alcohol groups, and aldo-keto isomerization. The energies were calculated for mainly aliphatic groups composed of carbon, hydrogen, and oxygen. The energy values showed that (1) when carbon-carbon bond cleavage involves two different types of functional groups, transfer of the shared electron-pair to the more reduced carbon group is energetically favored over transfer to the more oxidized carbon group, and (2) the energy of carbon-carbon bond transformation is strongly dependent on the type of functional group that donates the shared electron-pair during cleavage, and the group that accepts the shared electron-pair during synthesis, and (3) the energetics of C-C bond transformation is determined primarily by the half-reaction energies of the couples: carbonyl/carboxylic acid, carboxylic acid/carbon dioxide, alcohol/carbonyl, and hydrocarbon/alcohol. The energy of hydrogen-transfer between carbon groups was found to depend on the functional group class of both the hydrogen-donor and hydrogen-acceptor. From these and other observations we concluded that the chemistry of the origin of metabolism (and to a lesser degree modem metabolism) is strongly constrained by the (1) limited disproportionation energy of organic substrates that can be dissipated in a few irreversible reactions, (2) the energy-dominance of few half-reaction couples in carbon-carbon bond transformation that establishes whether a chemical reaction is energetically irreversible, reversible or unfeasible, and (3) the dependence of the transformation-energy on the oxidation state of carbon groups (functional group type) which is contingent on prior reactions in the synthetic pathway.
Weber, Arthur L.↗
Interstellar Deuterium Chemistry
The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer of interstellar components has been deuterium (D) excesses. In some cases these enrichments are seen in bulk meteoritic materials, but D enrichments have also been observed in meteoritic subfractions and even within specific classes of molecular species, such as amino and carboxylic acids. These anomalies are not thought to be the result of nucleosynthetic processes, but are instead ascribed to chemical and physical processes occurring in the interstellar medium (ISM). The traditional explanation of these D excesses has been to invoke the presence of materials made in the ISM by low temperature gas phase ion-molecule reactions. Indeed, the DM ratios seen in the simple interstellar gas phase molecules in cold dense clouds amenable to measurement using radio spectral techniques are generally considerably higher than the values seen in enriched Solar System materials. However, the true linkage between the DM ratios in interstellar and meteoritic materials is obscured by several effects. First, current observations of D enrichment in the ISM have been made of only a few simple molecules, molecules that are not the main carriers of D in Solar System materials. Second, some of the interstellar D enrichment is likely to reside on labile moieties that will have exchanged to some degree with more isotopically normal material during incorporation into the warm protosolar nebula, parent body processing, delivery, recovery, and analysis. Third, ion-molecule reactions represent only one of at least four processes that can produce strong D-H fractionation in the ISM.
Sandford, S. A.↗