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At least 109 records · Page 6

A possible role of fluctuating clay-water systems in the production of ordered prebiotic oligomers

A model is proposed for the intermediate stages of prebiotic evolution, based on the characteristics of the adsorption and condensation of amino acids and nucleotides on the surface area of clay minerals in a fluctuating environment. Template replication and translation of adsorbed oligonucleotides and catalytic effects by peptide products on further condensation are proposed, due to specific properties of hypohydrous clay surfaces as well as the biomolecules themselves. Experimental evidence supports some of the proposed interactions, and all of them can be tested experimentally.

Lahav, N.↗

The D/H ratio in Saturn's atmosphere from Voyager IRIS spectra

A selection of 1656 spectra recorded between 180 and 2300 mm in the 20 to 40 N latitude range by the Voyager interferometer IRIS were analyzed. The CH3D/H2 and CH4/H2 ratios are determined from a best fit of the radiances measured in the nu6 and nu4 fundamental bands, respectively centered at 1161 and 1304 mm. Results are CH3D/H2 = 3.9 + or - 2.5 times 10 to the minus 7th power and CH4/H2 = 4.5 + 2.4, -1.9 x 0.001. The uncertainty includes random errors due to instrumental noise and possible systematic errors in the assumed temperature profile and spectroscopic parameters. The D/H isotopic ratio is determined from abundance ratios from the expression D/H = 1/4f (CH3D/H2)/(CH4/H2) where f accounts for equilibrium deuterium fractionation between the molecular hydrogen and methane phases. Beer and Taylor (1973, 1978) estimated f = 1.37 + or - 0.07 for Jupiter assuming a wide range of convective velocities and neglecting catalytic effects from dust particles. The same value was adopted for Saturn and yields D/H = 1.6 +1.3, -1.2 times 10 to the minus 5th power.

Courtin, R.↗

Viscous-shock-layer analysis of hypersonic flows over long slender vehicles

An efficient and accurate method for solving the viscous shock layer equations for hypersonic flows over long slender bodies is presented. The two first order equations, continuity and normal momentum, are solved simultaneously as a coupled set. The flow conditions included are from high Reynolds numbers at low altitudes to low Reynolds numbers at high altitudes. For high Reynolds number flows, both chemical nonequilibrium and perfect gas cases are analyzed with surface catalytic effects and different turbulence models, respectively. At low Reynolds number flow conditions, corrected slip models are implemented with perfect gas case. Detailed comparisons are included with other predictions and experimental data.

Lee, Kam-Pui↗

Observations of Ozone-aerosol Correlated Behaviour in the Lower Stratosphere During the EASOE Campaign

The question of possible interactions between ozone and stratospheric aerosol has been open for a long time. Measurements carried out after the Mt. Agung and El Chicon eruptions showed evidence of negative correlations between the presence of volcanic stratospheric aerosols and ozone concentration. Evidence for negative correlations in the polar winter has been also found. It is only after the discovery of the Antarctic ozone hole that catalytic effects related to low temperature heterogeneous chemistry have become the object of much investigation, now extended to the role of volcanic aerosol in the ozone reduction. These phenomena can be the object of various interpretations, not mutually exclusive, including the effect of transport, diffuse radiation as well as heterogeneous chemistry. The present paper provides preliminary results of simultaneous measurements of ozone and aerosol, carried out at Thule, Greenland, during the winter 1991-92. The European Stratospheric Ozone Experiment (EASOE) was aimed at monitoring the winter Arctic stratosphere in order to obtain a deeper insight of the ozone destruction processes taking place in the polar regions. A large amount of aerosol was injected into the lower stratosphere by the recent eruption of Volcano Pinatubo. A lidar system, already operational in Thule since November 1990, has provided detailed measurements of the stratospheric aerosol concentration during EASOE. In the same period, a large number of ozonesondes were launched. Although no PSC formation was detected over Thule, the simultaneous measurement of the stratospheric aerosol and ozone profiles give the possibility to study interactions occurring in the stratosphere between these two constituents.

Digirolamo, P.↗

A novel approach to increasing cocaine detection confidence utilizing ion mobility spectrometry

When a positive detection of a narcotic occurs during the search of a vessel, a decision has to be made whether further intensive search is warranted. In terms of unwarranted delays of vessels and possible property damage, the accuracy of the analytical determination is very important. Analytical accuracy becomes critical when the data may be used in court actions as evidence. For this purpose, the U.S. Coast Guard has been investigating several confirmatory ion mobility spectrometry (IMS) field methods for the detection and identification of cocaine. This paper presents the findings of our investigations on the use of catalytic pyrolysis and base hydrolysis as confirmatory methods. The catalytic effects of various metals on the pyrolysis reaction are reported. In addition, the effects of several different ion mobility spectrometer sample transfer mediums and varying laboratory conditions on the base hydrolysis of the cocaine molecule are also be reported.

Jadamec, J. Richard↗

The nanosphere iron mineral(s) in Mars soil

A series of surface-modified clays containing nanophase (np) iron/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these 'Mars-soil analogs' were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxyl mineral such as 'green rust', or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable meaghemite (gamma-Fe203) by mild heat treatment and then to nanophase hematite (aplha-Fe203) by extensive heat treatment. Their chemical reactivity offers a plausible mechanism for the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxide and silicate phase surfaces. The mode of formation of these (nanophase) iron oxides on Mars is still unknown.

Banin, A.↗

Data Base for CFD Validation

The flow behind the shock wave formed around objects which fly at hypervelocity behaves differently from that of a perfect gas. Molecules become vibrationally excited, dissociated, and ionized. The hot gas may emit or absorb radiation. When the atoms produced by dissociation reach the wall surface, chemical reactions, including recombination, may occur. The thermochemical phenomena of vibration, dissociation, ionization, surface chemical reaction, and radiation are referred to commonly as high-temperature real-gas phenomena. The phenomena cause changes in the dynamic behavior of the flow and the surface pressure and heat transfer distribution around the object. The character of a real gas is described by the internal degrees of freedom and state of constituent molecules; nitrogen and oxygen for air. The internal energy states, rotation, vibration and electronic, of the molecules are excited and, in the limit, the molecular bonds are exceeded and the gas dissociated into atomic and, possibly, ionic constituents. The process of energy transfer causing excitation, dissociation and recombination is a rate process controlled by particle collisions. Binary, two-body, collisions are sufficient to cause internal excitation, dissociation and ionization while three-body collisions are required to recombine the particles into molecular constituents. If the rates of energy transfer are fast with respect to the local fluid dynamic time scale the gas is in, or nearly in, equilibrium. If the energy transfer rates are very slow the gas can be described as frozen. In all other instances, wherein any of the energy exchange rates are comparable to the local fluid time scale, the gas will be thermally or chemically reacting and out of equilibrium. Real gas thermochemical nonequilibrium processes are important in the determination of aerodynamic heating; both convective (including wall catalytic effects) and radiative heating. To illustrate this we consider the hypervelocity flow over a bluff body typical of an atmospheric entry vehicle or an aerospace transfer vehicle (ASTV). The qualitative aspects of a hypersonic flow field over a bluff body are discussed in two parts, forebody and afterbody, with attention to which particular physical effects must be included in an analysis. This will indicate what type of numerical modeling will be adequate in each region of the flow. A bluff forebody flow field is dominated by the presence of the strong bow shock wave and the consequent heating, and chemical reaction of the gas. At high altitude hypersonic flight conditions the thermal excitation and chemical reaction of the gas occur slowly enough that a significant portion of the flow field is in a state of thermochemical nonequilibrium. A second important effect is the presence of the thick boundary layer along the forebody surface. In this region there are large thermal and chemical species gradients due to the interaction of the gas with the wall. Also at high altitudes the shock wave and the boundary layer may become so thick that they merge; in this case the entire shock layer is dominated by viscous effects.

Deiwert, George S.↗

Thermal Protection Materials for Reentry and Planetary Applications

Thermal protection materials and systems (TPS) are used to protect spacecraft during reentry into Earth's atmosphere or entry into planetary atmospheres. As such, these materials are subject to severe environments with high heat fluxes and rapid heating. Catalytic effects can increase the temperatures substantially. These materials are also subject to impact damage from micrometeorites or other debris during ascent, orbit, and descent, and thus must be able to withstand damage and function following damage. Thermal protection materials and coatings used in reusable launch vehicles will be reviewed, including the needs and directions for new materials to enable new missions that require faster turnaround and much greater reusability. The role of ablative materials for use in high heat flux environments, especially for non-reusable applications and upcoming planetary missions, will be discussed. New thermal protection system materials may enable the use of sharp nose caps and leading edges on future reusable space transportation vehicles. Vehicles employing this new technology would have significant increases in maneuverability and out-of-orbit cross range compared to current vehicles, leading to increased mission safety in the event of the need to abort during ascent or from orbit. Ultrahigh temperature ceramics, a family of materials based on HfB2and ZrB2 with SiC, will be discussed. The development, mechanical and thermal properties, and uses of these materials will be reviewed.

Johnson, Sylvia M.↗

Polyimide Based Nanocomposites for Affordable Space Transport

In setting forth its strategic plan, NASA has indicated that low-cost access to space is the key to unleashing the commercial potential of space and greatly expanding space research and exploration. The development of advanced materials will be an enabling technology for this quest for low-cost space access. In this research program, we are attempting to address the need for new advanced materials by developing high-performance nanodispersed inorganic/organic and organic/organic polyimide composites utilizing specific interactions. Our goal is to systematically manipulate these interactions and investigate the resulting processing morphology-property relationships. Specifically, we will investigate three main parameters on these relationships. These include (1) the type of polyimide; (2) the structure of the inorganic nanoparticle being used; and (3) manipulation of the interfacial energy. During the first year of this effort, we have demonstrated the successful synthesis of PMR-15/layered silicate nanocomposites. Morphological studies indicate that exfoliated structures were obtained in most instances, with a mixture of exfoliated and intercalated structures being observed also. Significant enhancements of the onset of decomposition were obtained by varying the strength of the interaction between the nanoparticle and the polymer. Varying the amount of a specific nanoparticle also affected the decomposition temperatures. A slight catalytic effect of the nanoparticles on both the imidization and crosslinking reaction has been observed and will be presented. In addition, incorporation of the nanoparticles was found to increase the glass transition temperature and slightly broaden the breadth of this relaxation.

Dean, Derrick↗

Thermal Protection Materials for Reentry Applications

Thermal protection materials and systems (IRS) are used to protect spacecraft during reentry into Earth's atmosphere or entry into planetary atmospheres. As such, these materials are subject to severe environments with high heat fluxes and rapid heating. Catalytic effects can increase the temperatures substantially. These materials are also subject to impact damage from micrometeorites or other debris during ascent, orbit, and descent, and thus must be able to withstand damage and to function following damage. Thermal protection materials and coatings used in reusable launch vehicles will be reviewed, including the needs and directions for new materials to enable new missions that require faster turnaround and much greater reusability. The role of ablative materials for use in high heat flux environments, especially for non-reusable applications and upcoming planetary missions, will be discussed. New thermal protection system materials may enable the use of sharp nose caps and leading edges on future reusable space transportation vehicles. Vehicles employing this new technology would have significant increases in maneuverability and out-of-orbit cross range compared to current vehicles, leading to increased mission safety in the event of the need to abort during ascent or from orbit. Ultrahigh temperature ceramics, a family of materials based on HfB2 and ZrB2 with SiC, will be discussed. The development, mechanical and thermal properties, and uses of these materials will be reviewed.

Johnson, Sylvia M.↗

Evaluating experimental artifacts in hydrothermal prebiotic synthesis experiments

Control experiments with ultra pure deionized water were conducted to evaluate the organic contamination in hydrothermal prebiotic experiments. Different combinations of reaction vessel material, sampling tubing and stirring were tested and the amounts of organic contaminants determined. All tested types of polymer tubing were proven to introduce organic contaminants (formate, acetate and propionate ions) into the reacting solution. Stainless steel has a catalytic effect on the decomposition of formate, consistent with earlier work at high temperatures and pressures.

Equipment and Supplies↗

Quantum chemical studies of a model for peptide bond formation. 3. Role of magnesium cation in formation of amide and water from ammonia and glycine

The SN2 reaction between glycine and ammonia molecules with magnesium cation Mg2+ as a catalyst has been studied as a model reaction for Mg(2+)-catalyzed peptide bond formation using the ab initio Hartree-Fock molecular orbital method. As in previous studies of the uncatalyzed and amine-catalyzed reactions between glycine and ammonia, two reaction mechanisms have been examined, i.e., a two-step and a concerted reaction. The stationary points of each reaction including intermediate and transition states have been identified and free energies calculated for all geometry-optimized reaction species to determine the thermodynamics and kinetics of each reaction. Substantial decreases in free energies of activation were found for both reaction mechanisms in the Mg(2+)-catalyzed amide bond formation compared with those in the uncatalyzed and amine-catalyzed amide bond formation. The catalytic effect of the Mg2+ cation is to stabilize both the transition states and intermediate, and it is attributed to the neutralization of the developing negative charge on the electrophile and formation of a conformationally flexible nonplanar five-membered chelate ring structure.

Magnesium/chemistry↗

A Review of Hypersonics Aerodynamics, Aerothermodynamics and Plasmadynamics Activities within NASA's Fundamental Aeronautics Program

The research program of the aerodynamics, aerothermodynamics and plasmadynamics discipline of NASA's Hypersonic Project is reviewed. Details are provided for each of its three components: 1) development of physics-based models of non-equilibrium chemistry, surface catalytic effects, turbulence, transition and radiation; 2) development of advanced simulation tools to enable increased spatial and time accuracy, increased geometrical complexity, grid adaptation, increased physical-processes complexity, uncertainty quantification and error control; and 3) establishment of experimental databases from ground and flight experiments to develop better understanding of high-speed flows and to provide data to validate and guide the development of simulation tools.

Salas, Manuel D.↗

Very High Output Thermoelectric Devices Based on ITO Nanocomposites

A material having useful thermoelectric properties was synthesized by combining indium-tin-oxide (ITO) with a NiCoCrAlY alloy/alumina cermet. This material had a very large Seebeck coefficient with electromotive-force-versustemperature behavior that is considered to be excellent with respect to utility in thermocouples and other thermoelectric devices. When deposited in thin-film form, ceramic thermocouples offer advantages over precious-metal (based, variously, on platinum or rhodium) thermocouples that are typically used in gas turbines. Ceramic thermocouples exhibit high melting temperatures, chemical stability at high temperatures, and little or no electromigration. Oxide ceramics also resist oxidation better than metal thermocouples, cost substantially less than precious-metal thermocouples, and, unlike precious-metal thermocouples, do not exert catalytic effects.

Fralick, Gustave↗

Hydrogen Peroxide - Material Compatibility Studied by Microcalorimetry

Environmental and toxicity concerns with current hypergolic propellants have led to a renewed interest in propellant grade hydrogen peroxide (HP) for propellant applications. Storability and stability has always been an issue with HP. Contamination or contact of HP with metallic surfaces may cause decomposition, which can result in the evolution of heat and gas leading to increased pressure or thermal hazards. The NASA Johnson Space Center White Sands Test Facility has developed a technique to monitor the decompositions of hydrogen peroxide at temperatures ranging from 25 to 60 C. Using isothermal microcalorimetry we have measured decomposition rates at the picomole/s/g level showing the catalytic effects of materials of construction. In this paper we will present the results of testing with Class 1 and 2 materials in 90 percent hydrogen peroxide.

Homung, Steven D.↗

The Investigation of Chlorates as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detect-ed O2 and HCl gas releases from the Rocknest (RN) eolian bedform and the John Klein (JK) and Cumberland (CB) drill hole materials in Gale Crater. Chlorinated hydrocarbons have also been detected by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS). These detections along with the detection of perchlorate (ClO4-) by the Mars Phoenix Lander’s Wet Chemistry Laboratory (WCL) suggesting perchlorate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of perchlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. Iron mineralogy found in the Rocknest materials when mixed with Ca-perchlorate does cause O2 release temperatures to be closer match to the SAM O2 release data but more work is required in evaluating the catalytic effects of Fe mineralogy on perchlorate decomposition. Chlorates (ClO3-) are relevant Mars materials and potential O2 and Cl sources. The objective of this work is to evaluate the thermal decomposition of select chlorate (ClO3-) salts as possible sources of the O2 and HCl releases in the Gale Crater materials.

Sutter, B.↗

Towards Co-evolution of Membrane Transport and Metabolism

Protocellular boundaries were inextricably connected to the metabolism they encapsulated: to be inheritable, early metabolism must have led to an increased rate of growth and division of vesicles and, similarly, transport through vesicle boundaries must have supported the evolution of metabolism. Even though explaining how this coupling emerged and evolved in the absence of the complex machinery of modern cells is one of the key issues in studies on the origin of life, little is known about the biochemical and biophysical processes that might have been involved. This gap in our knowledge is a major impediment in efforts to construct scenarios for the origin of life and laboratory models of protocells. A combination of experimental and computational studies carried out by us and our collaborators is aimed at helping to close this gap. Properties of membranes might have contributed to the selection of RNA as an early biopolymer. A kinetic mechanism was proposed (Sacerdote & Szostak, 2005) in which ribose was supplied more quickly than other aldopentoses to primordial cells for preferential incorporation of ribonucleotides into nucleic acids. This proposal is based on a finding that ribose permeates membranes an order of magnitude faster than its diastereomers, arabinose and xylose. Our computer simulations, which yield permeation rates in excellent agreement with experiment, and kinetic modeling explain this phenomenon in terms of inter- and intramolecular interactions involving exocyclic hydroxyl groups attached to carbon atoms of the pyranose ring (Wei and Pohorille, 2009). They also constrain scenarios for the formation of the earliest nucleic acids (Wei and Pohorille, 2013). In one scenario, sugars permeate protocellular walls and subsequently are used to synthesize nucleic acids inside protocells. As long as this process proceeds at the rate faster than 6x10(exp -3)/s, ribose derivatives will be available for synthesis easier than their diastereomers. If nucleosides or their activated derivatives are synthesized outside protocells and subsequently transported across protocellular membranes the kinetic mechanism does not apply because all diastereomers, which have their sugars in the furanose rather than pyranose form, permeate the membrane at approximately the same rate. Properties of membranes might have been also coupled to metabolism involving peptides. Recently, Adamala and Szostak (2013) have shown that a dipeptide inside fatty-acid vesicles catalyzes the formation of another dipeptide that binds to vesicle walls and, by doing so, promotes their growth at the expense of other vesicles. This coupling of metabolism, permeability of vesicles and their growth is the first demonstration of evolutionary advantage imparted by small, membrane-bound peptides. Building on this work we have calculated the rate at which different blocked amino acids are delivered to a protocell for synthesis of dipeptides. We have further shown that the dipeptides are located at the water-membrane interface rather than in the center of the bilayer. On these basis it is anticipated that other dipeptides containing aromatic, but not necessarily hydrophobic amino acids (e.g. tyrosine) could have the same catalytic effects. Insight from these studies allows for estimating the rate of vesicle growth and the rates of dipeptide synthesis required to keep the system in balance. These results, in combination with our earlier studies, lead to a general scenario for evolution from membrane-bound dipeptides to ion channels in the origin of life.

Metabolism↗

Oxychlorine Species in Gale Crater and Broader Implications for Mars

Of 15 samples analyzed to date, the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) has detected oxychlorine compounds (perchlorate or chlorate) in 12 samples. The presence of oxychlorine species is inferred from the release of oxygen at temperatures less than 600degC and HCl between 350-850degC when a sample is heated to 850degC. The O2 release temperature varies with sample, likely caused by different cations, grain size differences, or catalytic effects of other minerals. In the oxychlorine-containing samples, perchlorate abundances range from 0.06 +/- 0.03 to 1.15 +/- 0.5 wt% Cl2O7 equivalent. Comparing these results to the elemental Cl concentration measured by the Alpha Particle X-ray Spectrometer (APXS) instrument, oxychlorine species account for 5-40% of the total Cl present. The variation in oxychlorine abundance has implications for their production and preservation over time. For example, the John Klein (JK) and Cumberland (CB) samples were acquired within a few meters of each other and CB contained approximately1.2 wt% Cl2O7 equivalent while JK had approximately 0.1 wt%. One difference between the two samples is that JK has a large number of veins visible in the drill hole wall, indicating more post-deposition alteration and removal. Finally, despite Cl concentrations similar to previous samples, the last three Murray formation samples (Oudam, Marimba, and Quela) had no detectable oxygen released during pyrolysis. This could be a result of oxygen reacting with other species in the sample during pyrolysis. Lab work has shown this is likely to have occurred in SAM but it is unlikely to have consumed all the O2 released. Another explanation is that the Cl is present as chlorides, which is consistent with data from the ChemCam (Chemical Camera) and CheMin (Chemistry and Mineralogy) instruments on MSL. For example, the Quela sample has approximately1 wt% elemental Cl detected by APXS, had no detectable O2 released, and halite (NaCl) has been tentatively identified in CheMin X-ray diffraction data. These data show that oxychlorines are likely globally distributed on Mars but the distribution is heterogenous depending on the perchlorate formation mechanism (production rate), burial, and subsequent diagenesis

Ming, Douglas W.↗