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At least 37 records · Page 2

Terrestrial evolution of polymerization of amino acids - Heat to ATP

Sets of amino acids containing sufficient trifunctional monomer are thermally polymerized at temperatures such as 65 deg; the amino acids order themselves. Various polymers have diverse catalytic activities. The polymers aggregate, in aqueous solution, to cell-like structures having those activities plus emergent properties, e.g. proliferatability. Polyamino acids containing sufficient lysine catalyze conversion of free amino acids, by ATP, to small peptides and a high molecular weight fraction. The lysine-rich proteinoid is active in solution, within suspensions of cell-like particles, or in other particles composed of lysine-rich proteinoid and homopolyribonucleotide. Selectivities are observed. An archaic polyamino acid prelude to coded protein synthesis is indicated.

Fox, S. W.↗

Some analyses of the chemistry and diffusion of SST exhaust materials during phase 3 of the wake period

In the generally stably stratified lower stratosphere, SST exhaust plumes could spend a significant length of time in a relatively undispersed state. This effort has utilized invariant modeling techniques to simulate the separate and combined effects of atmospheric turbulence, turbulent diffusion, and chemical reactions of SST exhaust materials in the lower stratosphere. The primary results to date are: (1) The combination of relatively slow diffusive mixing and rapid chemical reactions during the Phase III wake period minimizes the effect of SST exhausts on O3 depletion by the so-called NOx catalytic cycle. While the SST-produced NO is substantially above background concentrations, it appears diffusive mixing of NO and O3 is simply too slow to produce the O3 depletions originally proposed. (2) The time required to dilute the SST exhaust plume may be a significant fraction of the total time these materials are resident in the lower stratosphere. If this is the case, then prior estimates of the environmental impact of these materials must be revised significantly downward.

Hilst, G. R.↗

Catalytic Oxidation of CO for Closed-Cycle CO2 Lasers

Stoichiometric mixture converted completely. High-energy pulsed CO2 lasers have potential for measuring many different features of atmosphere of Earth and particularly useful on airborne or space platforms. For this application, laser must be operated in closed cycle to conserve gas, especially if rare nonradioactive isotopes of carbon and oxygen used. However, laser discharge decomposes fraction of CO2 to CO and O2, causing rapid loss in power leading to erratic behavior. To maintain operation, CO and O2 must be recombined to form CO2.

Miller, I. M.↗

A multiblock analysis for shuttle orbiter re-entry heating from Mach 24 to Mach 12

A multiblock, laminar heating analysis for the shuttle orbiter at three trajectory points ranging from Mach 24.3 to Mach 12.86 on re-entry is described. The analysis is performed using the Langley Aerothermodynamic Upwind Relaxation Algorithm (LAURA) with both a seven species chemical nonequilibrium model and an equilibrium model. A finite-catalytic-wall model appropriate for shuttle tiles at a radiative equilibrium wall temperature is applied. Computed heating levels are generally in good agreement with the flight data though a few rather large discrepancies remain unexplained. The multiblock relaxation strategy partitions the flowfield into manageable blocks requiring a fraction of the computational resources (time and memory) required by a full domain approach. In hot, the computational cost for a solution at even a single trajectory point would be prohibitively expensive at the given resolution without the multiblock approach. Converged blocks are reassembled to enable a fully coupled converged solution over the entire vehicle, starting from a nearly converged initial condition.

Gnoffo, Peter A.↗

Summertime partitioning and budget of NO(y) compounds in the troposphere over Alaska and Canada: ABLE 3B

As part of NASA's Arctic Boundary Layer Expedition 3A and 3B field measurement programs, measurements of NO(x), HNO3, PAN, PPN, and NO(y) were made in the middle to lower troposphere over Alaska and Canada during the summers of 1988 and 1990. These measurements are used to assess the degree of closure within the reactive odd nitrogen (N(x)O(y)) budget through the comparison of the values of NO(y) measured with a catalytic convertor to the sum of individually measured NO(y) (i) compounds (i.e., sigmaNO(y)(i) = NO(x) + HNO3 + PAN + PPN). Significant differences were observed between the various study regions. In the lower 6 km of the troposphere over Alaska and the Hudson Bay lowlands of Canada a significant fraction of the NO(y) budget (30 to 60%) could not be accounted for by the measured sigmaNO(y)i. This deficit in the NO(y) budget is about 100 to 200 parts per trillion by volume (pptv) in the lower troposphere (0.15 to 3 km) and about 200 to 400 pptv in the middle free troposphere (3 to 6.2 km). Conversely, the NO(y) budget in the northern Labrador and Quebec regions of Canada is almost totally accounted for within the combined measurement uncertainties of NO(y) and the various NO(y)(i) compounds. A substantial portion of the NO(y) budget's 'missing compounds' appears to be coupled to the photochemical and/or dynamical parameters influencing the tropospheric oxidative potential over these regions. A combination of factors are suggested as the causes for the variability observed in the NO(y) budget. In addition, the apparent stability of compounds represented by the NO(y) budget deficit in the lower-altitude range questions the ability of these compounds to participate as reversible reservoirs for 'active' odd nitrogen and suggest that some portion of the NO(y) budget may consist of relatively unreactive nitrogen-containing compounds.

Sandholm, S.↗

A preliminary sensitivity analysis of the coupled diffusion and chemistry model

The sensitivity of the coupled chemistry/diffusion model's outputs to a wide range of variation of the model's independent variables has been investigated. It is shown that the efficiency with which the now catalytic cycle destroys ambient O3 is extremely sensitive to the amount of NO emitted and to the relative rates of turbulent diffusion and chemical reactions. For representative conditions in the stratosphere, a tenfold variation of either the turbulence intensity or the reaction rate constant or the source strength can vary the efficiency from 1% to 50%. If the duration of Phase 3 is a significant fraction of the total residence time of the plume, then these efficiency variations can alter O3 depletion rates by more than a factor of two. These results, therefore, point toward those variables which must be accurately defined or measured if one is to adequately predict the effect of SST operations on the ambient inventory of O3 in the lower stratosphere.

Hilst, G. R.↗

Correlations of catalytic combustor performance parameters

Correlations for combustion efficiency percentage drop and the minimum required adiabatic reaction temperature necessary to meet emissions goals of 13.6 g CO/kg fuel and 1.64 g HC/kg fuel are presented. Combustion efficiency was found to be a function of the cell density, cell circumference, reactor length, reference velocity, and adiabatic reaction temperature. The percentage pressure drop at an adiabatic reaction temperature of 1450 K was found to be proportional to the reference velocity to the 1.5 power and to the reactor length. It is inversely proportional to the pressure, cell hydraulic diameter, and fractional open area. The minimum required adiabatic reaction temperature was found to increase with reference velocity and decrease with cell circumference, cell density and reactor length. A catalyst factor was introduced into the correlations to account for differences between catalysts. Combustion efficiency, the percentage pressure drop, and the minimum required adiabatic reaction temperature were found to be a function of the catalyst factor. The data was from a 12 cm-diameter test rig with noble metal reactors using propane fuel at an inlet temperature of 800 K.

Bulzan, D. L.↗

Exploring Connectivity in Sequence Space of Functional RNA

Emergence of replicable genetic molecules was one of the marking points in the origin of life, evolution of which can be conceptualized as a walk through the space of all possible sequences. A theoretical concept of fitness landscape helps to understand evolutionary processes through assigning a value of fitness to each genotype. Then, evolution of a phenotype is viewed as a series of consecutive, single-point mutations. Natural selection biases evolution toward peaks of high fitness and away from valleys of low fitness. whereas neutral drift occurs in the sequence space without direction as mutations are introduced at random. Large networks of neutral or near-neutral mutations on a fitness landscape, especially for sufficiently long genomes, are possible or even inevitable. Their detection in experiments, however, has been elusive. Although a few near-neutral evolutionary pathways have been found, recent experimental evidence indicates landscapes consist of largely isolated islands. The generality of these results, however, is not clear, as the genome length or the fraction of functional molecules in the genotypic space might have been insufficient for the emergence of large, neutral networks. Thorough investigation on the structure of the fitness landscape is essential to understand the mechanisms of evolution of early genomes. RNA molecules are commonly assumed to play the pivotal role in the origin of genetic systems. They are widely believed to be early, if not the earliest, genetic and catalytic molecules, with abundant biochemical activities as aptamers and ribozymes, i.e. RNA molecules capable, respectively, to bind small molecules or catalyze chemical reactions. Here, we present results of our recent studies on the structure of the sequence space of RNA ligase ribozymes selected through in vitro evolution. Several hundred thousands of sequences active to a different degree were obtained by way of deep sequencing. Analysis of these sequences revealed several large clusters defined such that every sequence in a cluster can be reached from any other sequence in the same cluster through a series of single point mutations. Sequences in a single cluster appear to adopt more than one secondary structure. The mechanism of refolding within a single cluster was examined. To shed light on possible evolutionary paths in the space of ribozymes, the connectivity between clusters was investigated. The effect of length of RNA molecules on the structure of the fitness landscape and possible evolutionary paths was examined by way of comparing functional sequences of 20 and 80 nucleobases in length. It was found that sequences of different lengths shared secondary structure motifs that were presumed responsible for catalytic activity, with increasing complexity and global structural rearrangements emerging in longer molecules.

Wei, Chenyu↗

Viscous reacting flows with wall slip and catalysis applied to spheres in arc jets and flight

The influence of wall slip and catalytic atom-recombination on the flow field and wall heat flux are calculated for high altitude flight and arc jet flow conditions. Boundary equations, which include velocity slip, temperature jump, and wall catalytic atom recombination, are coupled to the viscous reacting multicomponent Navier-Stokes equations. These equations are solved using a time-dependent finite difference technique applied to spheres in an arc jet flow (Reynolds number of 550) and a high altitude flight case representative of the Space Shuttle Orbiter (Reynolds number of 450). The results indicate that catalysis strongly influences the temperature jump, but not the velocity slip. Slip increases the atom fraction and temperature at both the wall and the flow field. Likewise, the shock stand-off distance, the wall heat flux, and friction coefficient are increased over the nonslip cases. The reacting gas calculations confirm the chemically frozen nature of the shock layer in arc jet flows.

Scott, C. D.↗

Laboratory Studies of Fischer-Tropsch-Type Reactions and Their Implications for Organics in Asteroids and Comets

We have been studying Fischer-Tropsch type (FTT) reactions as a source for organic materials both in the gas phase of the solar nebula and incorporated into primitive comets and asteroids for almost 10 years, and over this time our concept has evolved greatly from the standard "catalytic" model to a much more robust chemical scenario. Our simulations have been conducted at temperatures that are much higher than we like, primarily for practical reasons such as the timescale of individual reactions, and we are just starting a series of measurements to allow us to measure reaction rates at temperatures from 873K down to as low as 373K. We have preliminary data on the carbon (d13C = -50) & nitrogen (d15N = +9.5) isotopic fractionation at 873K, but not on materials produced at lower temperature. Isotope values are on the VPDB scale for carbon and vs. Air for nitrogen. We have also investigated the noble gas trapping efficiency of the FTT process by adding a small amount of a noble gas mix to our standard synthesis mix. The noble gas ratio is 49:49:1:1::Ne:Ar:Kr:Xe. Xe and Kr are trapped at 873K and are more efficiently trapped at 673K with no isotopic fractionation at either temperature. Ar trapping is detected at 673K, but not at 873K. Ne has not yet been observed in our samples. The solar nebula was an extremely complex system, mixing materials from the innermost regions out to well into the zones where comets formed and thus mixing highly processed nebular materials with grains and coatings formed before the nebula began to collapse. Laboratory studies may provide the means to separate such diverse components based on carbon or nitrogen isotopic fractionation or the quantities of noble gases trapped in grain coatings and their thermal release patterns, among other observables. The ultimate goal of laboratory synthesis of nebular analogs is to provide the means to identifY the conditions under which natural samples were formed and the signatures of subsequent metamorphic events.

Nuth, Joseph↗

Method of Heating a Foam-Based Catalyst Bed

A method of heating a foam-based catalyst bed has been developed using silicon carbide as the catalyst support due to its readily accessible, high surface area that is oxidation-resistant and is electrically conductive. The foam support may be resistively heated by passing an electric current through it. This allows the catalyst bed to be heated directly, requiring less power to reach the desired temperature more quickly. Designed for heterogeneous catalysis, the method can be used by the petrochemical, chemical processing, and power-generating industries, as well as automotive catalytic converters. Catalyst beds must be heated to a light-off temperature before they catalyze the desired reactions. This typically is done by heating the assembly that contains the catalyst bed, which results in much of the power being wasted and/or lost to the surrounding environment. The catalyst bed is heated indirectly, thus requiring excessive power. With the electrically heated catalyst bed, virtually all of the power is used to heat the support, and only a small fraction is lost to the surroundings. Although the light-off temperature of most catalysts is only a few hundred degrees Celsius, the electrically heated foam is able to achieve temperatures of 1,200 C. Lower temperatures are achievable by supplying less electrical power to the foam. Furthermore, because of the foam s open-cell structure, the catalyst can be applied either directly to the foam ligaments or in the form of a catalyst- containing washcoat. This innovation would be very useful for heterogeneous catalysis where elevated temperatures are needed to drive the reaction.

Fortini, Arthur J.↗

A carbon-13 and proton nuclear magnetic resonance study of some experimental referee broadened-specification /ERBS/ turbine fuels

Preliminary results of a nuclear magnetic resonance (NMR) spectroscopy study of alternative jet fuels are presented. A referee broadened-specification (ERBS) aviation turbine fuel, a mixture of 65 percent traditional kerosene with 35 percent hydrotreated catalytic gas oil (HCGO) containing 12.8 percent hydrogen, and fuels of lower hydrogen content created by blending the latter with a mixture of HCGO and xylene bottoms were studied. The various samples were examined by carbon-13 and proton NMR at high field strength, and the resulting spectra are shown. In the proton spectrum of the 12.8 percent hydrogen fuel, no prominent single species is seen while for the blending stock, many individual lines are apparent. The ERBS fuels were fractionated by high-performance liquid chromatography and the resulting fractions analyzed by NMR. The species found are identified.

Dalling, D. K.↗

Properties of grains derived from IRAS observations of dust

The authors used the results of Infrared Astronomy Satellite (IRAS) observations of diffuse medium dust to develop a theoretical model of the infrared properties of grains. Recent models based entirely on traditional observations of extinction and polarization include only particles whose equilibrium temperatures do not exceed 20 K in the diffuse interstellar medium. These classical grains, for which the authors have adopted the multipopulation model developed by Hong and Greenberg (1980), can explain only the emission in the IRAS 100 micron band. The measurements at shorter wavelengths (12, 25 and 60 microns) require two new particle populations. Vibrational fluorescence from aromatic molecules provides the most likely explanation for the emission observed at 12 microns, with polycyclic aeromatic hydrocarbons (PAHs) containing about 10 percent of cosmic carbon. A simplified model of the emission process shows that PAH molecules can also explain most of the emission measured by IRAS at 25 microns. The authors identified the warm particles responsible for the excess 60 microns emission with small (a approx. equals 0.01 microns) iron grains. A compilation of the available data on the optical properties of iron indicates that the diffuse medium temperature of small iron particles should be close to 50 K and implies that a large, possibly dominant, fraction of cosmic iron must be locked up in metallic particles in order to match the observed 60 microns intensities. The model matches the infrared fluxes typically observed by IRAS in the diffuse medium and can also reproduce the infrared surface brightness distribution in individual clouds. In particular, the combination of iron and classical cool grains can explain the surprising observations of the 60/100 microns flux ratio in clouds, which is either constant or increases slightly towards higher opacities. The presence of metallic grains has significant implications for the physics of the interstellar medium, including catalytic H2 formation, for which iron grains could be the main site; differences in depletion patterns between iron and other refractory elements (Mg, Si); and superparamagnetic behavior of large grains with embedded iron clusters giving rise to the observed high degree of alignment by the galactic magnetic field.

Wesselius, P. R.↗

Correlations of catalytic combustor performance parameters

A 12-cm-diameter catalytic combustor test rig using propane fuel at an inlet temperature of 800 K, a pressure of 300,000 Pa, and reference velocities from 10 to 20 m/s was studied. Combustion efficiency at the test conditions is a function of the catalyst bed cell density, cell circumference, reactor length, and the reference velocity; the efficiency was also dependent on the adiabatic reaction temperature to the tenth power. The percentage pressure drop is proportional to the reference velocity to the 1.5 power and is also proportional to the reactor length and inversely proportional to the cell hydraulic diameter, fractional open area, and the pressure. The minimum adiabatic reaction temperature required to meet the emissions goals is proportional to the reference velocity to the 0.1 power and inversely proportional to the cell circumference, cell density, and reactor length to the 0.1 power. The parameters which are a function of a catalyst factor are reported.

Bulzan, D. L.↗

Effects of Surface Recombination on Heat Transfer to Bodies in a High Enthalpy Stream of Partially Dissociated Nitrogen

Heat-transfer rates to two surfaces having widely different catalytic effectiveness are compared at a Mach number of 6 in a low-density stream of partially dissociated nitrogen. The heat-transfer rate to a polished copper cylinder is twice as great as the heat-transfer rate to a silicon-monoxide-coated cylinder when the stream total energy content is 9000 Btu/lb. Various methods for determining the stream energy content, the stream velocity, and the stream Mach number have been developed and compared. It is shown that methods for estimating the stream energy content by means of purely aerodynamic concepts may neglect the sizable fraction of the stream energy contained in molecular dissociation.

Winkler, Ernest L..↗

Purification and characterization of a casein kinase 2-type protein kinase from pea nuclei

Almost all the polyamine-stimulated protein kinase activity associated with the chromatin fraction of nuclei purified from etiolated pea (Pisum sativum L.) plumules is present in a single enzyme that can be extracted from chromatin by 0.35 molar NaCl. This protein kinase can be further purified over 2000-fold by salt fractionation and anion-exchange and casein-agarose column chromatography, after which it is more than 90% pure. The purified kinase has a specific activity of about 650 nanomoles per minute per milligram protein in the absence of polyamines, with either ATP or GTP as phosphoryl donor. Spermidine can stimulate its activity fourfold, with half-maximal activation at about 2 millimolar. Spermine and putrescine also stimulate activity, although somewhat less effectively. This kinase has a tetrameric alpha 2 beta 2 structure with a native molecular weight of 130,000, and subunit molecular weights of 36,000 for the catalytic subunit (alpha) and 29,000 for the regulatory subunit (beta). In western blot analyses, only the alpha subunit reacts strongly with polyclonal antibodies to a Drosophila casein kinase II. The pea kinase can use casein and phosvitin as artificial substrates, phosphorylating both the serine and threonine residues of casein. It has a pH optimum near 8.0, a Vmax of 1.5 micromoles per minute per milligram protein, and a Km for ATP of approximately 75 micromolar. Its activity can be almost completely inhibited by heparin at 5 micrograms per milliliter, but is relatively insensitive to concentrations of staurosporine, K252a, and chlorpromazine that strongly antagonize Ca(2+) -regulated protein kinases. These results are discussed in relation to recent findings that casein kinase 2-type kinases may phosphorylate trans-acting factors that bind to light-regulated promoters in plants.

NASA Program Space Biology↗

Antarctic stratospheric chemistry of chlorine nitrate, hydrogen chloride, and ice - Release of active chlorine

The reaction rate between atmospheric hydrogen chloride (HCl) and chlorine nitrate (ClONO2) is greatly enhanced in the presence of ice particles; HCl dissolves readily into ice, and the collisional reaction probability for ClONO2 on the surface of ice with HCl in the mole fraction range from about 0.003 to 0.010 is in the range from about 0.05 to 0.1 for temperatures near 200 K. Chlorine is released into the gas phase on a time scale of at most a few milliseconds, whereas nitric acid (HNO3), the other product, remains in the condensed phase. This reaction could play an important role in explaining the observed depletion of ozone over Antarctica; it releases photolytically active chlorine from its most abundant reservoir species, and it promotes the formation of HNO3 and thus removes nitrogen dioxide from the gas phase. Hence it establishes the necessary conditions for the efficient catalytic destruction of ozone by halogenated free radicals.

Molina, Mario J.↗

Requirements for the early atmosphere of Mars from nitrogen isotope ratios

The N escape models of Fox and Dalgarno and Fox required the presence of a dense, early CO2 atmosphere to inhibit fractionation of the N isotopes N-15 and N-14. The computed photochemical escape fluxes are so large at the present that the isotope ratio measured by Viking (about 1.62x terrestrial) can be produced in about 1.5 b.y. This model was refined in several ways. It was updated to incorporate the variation of the escape fluxes with increases in the solar fluxes at earlier times according to the model of Zahnle and Walker. As expected, this exacerbates the problem with overfractionation, but not greatly. Most of the escape and fractionation of the N occurs in the last 1.5 b.y., when the solar flux was only slightly different from the present. The dense early atmosphere must persist only a bit longer in order to reproduce the measured isotope ratio. The model was also modified to take into account changes in the O mixing ratio with time in the past, assuming that the O abundance is proportional to the square root of the solar flux. Although the production rate of O from photodissociation of CO2 scales as the solar flux, the strength of the winds and other mixing processes also increases with the solar flux, resulting in possibly more effective transport of O to the lower atmosphere where it is destroyed by catalytic and three-body recombination mechanisms.

Fox, J. L.↗