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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1980

Study of catalyst cured LaRC-160/Celion 6000 composites

LaRC 160 polyimide was modified with a high temperature peroxide catalyst, USP-138, in an attempt to reduce the final cure temperature to below 316 C. This effort was directed at obtaining a material for 177 C use that would cure at similar temperatures to a high performance epoxy while still maintaining the good moisture resistance of a polymide material. Attempts to prepare a laminate made from Celion 6000 fiber and 5% catalyzed LaRC 160 resin gave a material with minimal properties after curing at 193 C. Acceptable properties were not obtained until a final cure temperature of 260 C was used. A control laminate containing no catalyst and cured under the same conditions had only half the level of shear strength. The catalyzed LaRC 160 prepreg was also used to examine the possibility of shortening the conventional LaRC 160 cure at 316 C. Maximum properties were obtained using a 2.5% catalyzed product with a final cure temperature of 316 C held for fifteen minutes. Differences in properties between catalyzed and uncatalyzed product disappeared, however, when the cure time at 316 C was extended to 45 minutes.

Edelman, R.↗
NASA NTRS1993

Applicability of PM3 to transphosphorylation reaction path: Toward designing a minimal ribozyme

A growing body of evidence shows that RNA can catalyze many of the reactions necessary both for replication of genetic material and the possible transition into the modern protein-based world. However, contemporary ribozymes are too large to have self-assembled from a prebiotic oligonucleotide pool. Still, it is likely that the major features of the earliest ribozymes have been preserved as molecular fossils in the catalytic RNA of today. Therefore, the search for a minimal ribozyme has been aimed at finding the necessary structural features of a modern ribozyme (Beaudry and Joyce, 1990). Both a three-dimensional model and quantum chemical calculations are required to quantitatively determine the effects of structural features of the ribozyme on the reaction it catalyzes. Using this model, quantum chemical calculations must be performed to determine quantitatively the effects of structural features on catalysis. Previous studies of the reaction path have been conducted at the ab initio level, but these methods are limited to small models due to enormous computational requirements. Semiempirical methods have been applied to large systems in the past; however, the accuracy of these methods depends largely on a simple model of the ribozyme-catalyzed reaction, or hydrolysis of phosphoric acid. We find that the results are qualitatively similar to ab initio results using large basis sets. Therefore, PM3 is suitable for studying the reaction path of the ribozyme-catalyzed reaction.

Manchester, John I.↗
NASA NTRS2001

The sugar model: catalysis by amines and amino acid products

Ammonia and amines (including amino acids) were shown to catalyze the formation of sugars from formaldehyde and glycolaldehyde, and the subsequent conversion of sugars to carbonylcontaining products under the conditions studied (pH 5.5 and 50 degrees C). Sterically unhindered primary amines were better catalysts than ammonia, secondary amines, and sterically hindered primary amines (i.e. alpha-aminoisobutyric acid). Reactions catalyzed by primary amines initially consumed formaldehyde and glycolaldehyde about 15-20 times faster than an uncatalyzed control reaction. The amine-catalyzed reactions yielded aldotriose (glyceraldehyde), ketotriose (dihydroxyacetone), aldotetroses (erythrose and threose), ketotetrose (erythrulose), pyruvaldehyde, acetaldehyde, glyoxal, pyruvate, glyoxylate, and several unindentified carbonyl products. The concentrations of the carbonyl products, except pyruvate and ketotetrose, initially increased and then declined during the reaction, indicating their ultimate conversion to other products (like larger sugars or pyruvate). The uncatalyzed control reaction yielded no pyruvate or glyoxylate, and only trace amounts of pyruvaldehyde, acetaldehyde and glyoxal. In the presence of 15 mM catalytic primary amine, such as alanine, the rates of triose and pyruvaldehyde of synthesis were about 15-times and 1200-times faster, respectively, than the uncatalyzed reaction. Since previous studies established that alanine is synthesized from glycolaldehyde and formaldehyde via pyruvaldehyde as its direct precursor, the demonstration that the alanine catalyzes the conversion of glycolaldehyde and formaldehyde to pyruvaldehyde indicates that this synthetic pathway is capable of autocatalysis. The relevance of this synthetic process, named the Sugar Model, to the origin of life is discussed.

Acetaldehyde/analogs & derivatives/chemistry↗
NASA NTRS1984

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↗
NASA NTRS1997

Isolation of novel ribozymes that ligate AMP-activated RNA substrates

BACKGROUND: The protein enzymes RNA ligase and DNA ligase catalyze the ligation of nucleic acids via an adenosine-5'-5'-pyrophosphate 'capped' RNA or DNA intermediate. The activation of nucleic acid substrates by adenosine 5'-monophosphate (AMP) may be a vestige of 'RNA world' catalysis. AMP-activated ligation seems ideally suited for catalysis by ribozymes (RNA enzymes), because an RNA motif capable of tightly and specifically binding AMP has previously been isolated. RESULTS: We used in vitro selection and directed evolution to explore the ability of ribozymes to catalyze the template-directed ligation of AMP-activated RNAs. We subjected a pool of 10(15) RNA molecules, each consisting of long random sequences flanking a mutagenized adenosine triphosphate (ATP) aptamer, to ten rounds of in vitro selection, including three rounds involving mutagenic polymerase chain reaction. Selection was for the ligation of an oligonucleotide to the 5'-capped active pool RNA species. Many different ligase ribozymes were isolated; these ribozymes had rates of reaction up to 0.4 ligations per hour, corresponding to rate accelerations of approximately 5 x10(5) over the templated, but otherwise uncatalyzed, background reaction rate. Three characterized ribozymes catalyzed the formation of 3'-5'-phosphodiester bonds and were highly specific for activation by AMP at the ligation site. CONCLUSIONS: The existence of a new class of ligase ribozymes is consistent with the hypothesis that the unusual mechanism of the biological ligases resulted from a conservation of mechanism during an evolutionary replacement of a primordial ribozyme ligase by a more modern protein enzyme. The newly isolated ligase ribozymes may also provide a starting point for the isolation of ribozymes that catalyze the polymerization of AMP-activated oligonucleotides or mononucleotides, which might have been the prebiotic analogs of nucleoside triphosphates.

NASA Discipline Exobiology↗
NASA NTRS1972

Study of the techniques feasible for food synthesis aboard a spacecraft

Synthesis of sugars by Ca(OH)2 catalyzed formaldehyde condensation (the formose reaction) has produced branched carbohydrates that do not occur in nature. The kinetics and mechanisms of the homogeneously catalyzed autocatalytic condensation were studied and analogies between homogeneous and heterogeneous rate laws have been found. Aldol condensations proceed simultaneously with Cannizzaro and crossed-Cannizzaro reactions and Lobry de Bruyn-Van Eckenstein rearrangements. The separate steps as well as the interactions of this highly complex reaction system were elucidated. The system exhibits instabilities, competitive catalytic, mass action, and equilibrium phenomena, complexing, and parallel and consecutive reactions. Specific finding that have been made on the problem will be of interest for synthesizing sugars, both for sustained space flight and for large scale food manufacture. A contribution to methodology for studying complex catalyzed reactions and to understanding control of reaction selectivity was a broad goal of the project.

Weiss, A. H.↗
NASA NTRS1984

Development of electrodes for the NASA iron/chromium

This program was directed primarily to the development of the negative (Cr3+/Cr2+) electrode for the NASA chromous/ferric Redox battery. The investigation of the effects of substrate processing and gold/lead catalyzation parameters on electrochemical performance were continued. In addition, the effects of reactant cross-mixing, acidity level, and temperature were examined for both Redox couples. Finally, the performance of optimized electrodes was tested in system hardware (1/3 square foot single cell). The major findings are discussed: (1) The recommended processing temperature for the carbon felt, as a substrate for the negative electrode, is 1650 to 1750 C, (2) The recommended gold catalyzation procedure is essentially the published NASA procedure (NASA TM-82724, Nov. 1981) based on deposition from aqueous methanol solution, with the imposition of a few controls such as temperature (25 C) and precatalyzation pH of the felt (7), (3) Experimental observations of the gold catalyzation process and subsequent electron microscopy indicate that the gold is deposited from the colloidal state, induced by contact of the solution with the carbon felt, (4) Electrodeposited lead appears to be present as a thin uniform layer over the entire surface of the carbon fibers, rather than an discrete particles, and (5) Cross-mixing of reactants (Fe-2+ in negative electrode solution or Cr-3+ in the positive electrode solution) did not appear to produce significant interference at either electrode.

Swette, L.↗
NASA NTRS1987

Organometallic catalysts for primary phosphoric acid fuel cells

A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.

Walsh, Fraser↗
NASA NTRS1996

Bromine-Chlorine Coupling in the Antarctic Ozone Hole

The contribution from the chlorine and bromine species in the formation of the Antarctic ozone hole is evaluated. Since chlorine and bromine compounds are of different industrial origin, it is desirable, from a policy point of view, to be able to attribute chlorine-catalyzed loss of ozone with those reactions directly involving chlorine species, and likewise for bromine-catalyzed loss. In the stratosphere, however, most of the chemical families are highly coupled, and, for example, changes in the chlorine abundance will alter the partitioninig in other families and thus the rate of ozone loss. This modeling study examines formation of the Antarctic ozone hole for a wide range of bromine concentrations (5 - 25 pptv) and for chlorine concentrations typical of the last two decades (1.5, 2.5 and 3.5 ppbv). We follow the photochemical evolution of a single parcel of air, typical of the inner Antarctic vortex (50 mbar, 70 deg. S, NO(sub y) = 2 ppbv, with Polar Stratospheric Clouds(PSC)) from August 1 to November 1. For all of these ranges of chlorine and bromine loading, we would predict a substantial ozone hole (local depletion greater than 90%) within the de-nitrified, PSC- perturbed vortex. The contributions of the different catalytic cycles responsible for ozone loss are tabulated. The deep minimum in ozone is driven primarily by the chlorine abundance. As bromine levels decrease, the magnitude of the chlorine-catalyzed ozone loss increases to take up the slack. This is because bromine suppresses ClO by accelerating the conversion of ClO an Cl2O2 back to HCI. For this range of conditions, the local relative efficiency of ozone destruction per bromine atom to that per chlorine atom (alpha-factor) ranges from 33 to 55, decreasing with increase of bromine.

Danilin, Michael Y.↗
NASA NTRS1990

Isomerization of 1-O-indol-3-ylacetyl-beta-D-glucose. Enzymatic hydrolysis of 1-O, 4-O, and 6-O-indol-3-ylacetyl-beta-D-glucose and the enzymatic synthesis of indole-3-acetyl glycerol by a hormone metabolizing complex

The first compound in the series of reactions leading to the ester conjugates of indole-3-acetic acid (IAA) in kernels of Zea mays sweet corn is the acyl alkyl acetal, 1-O-indol-3-ylacetyl-beta-D-glucose (1-O-IAGlu). The enzyme catalyzing the synthesis of this compound is UDP-glucose:indol-3-ylacetate glucosyl-transferase (IAGlu synthase). The IAA moiety of the high energy compound 1-O-IAGlu may be enzymatically transferred to myo-inositol or to glycerol or the 1-O-IAGlu may be enzymatically hydrolyzed. Alternatively, nonenzymatic acyl migration may occur to yield the 2-O, 4-O, and 6-O esters of IAA and glucose. The 4-O and 6-O esters may then be enzymatically hydrolyzed to yield free IAA and glucose. This work reports new enzymatic activities, the transfer of IAA from 1-O-IAGlu to glycerol, and the enzyme-catalyzed hydrolysis of 4-O and 6-O-IAGlu. Data is also presented on the rate of non-enzymatic acyl migration of IAA from the 1-O to the 4-O and 6-O positions of glucose. We also report that enzymes catalyzing the synthesis of 1-O-IAGlu and the hydrolysis of 1-O, 4-O, and 6-O-IAGlu fractionate as a hormone metabolizing complex. The association of synthetic and hydrolytic capabilities in enzymes which cofractionate may have physiological significance.

Non-NASA Center↗
NASA NTRS2001

Ultra precision and reliable bonding method

The bonding of two materials through hydroxide-catalyzed hydration/dehydration is achieved at room temperature by applying hydroxide ions to at least one of the two bonding surfaces and by placing the surfaces sufficiently close to each other to form a chemical bond between them. The surfaces may be placed sufficiently close to each other by simply placing one surface on top of the other. A silicate material may also be used as a filling material to help fill gaps between the surfaces caused by surface figure mismatches. A powder of a silica-based or silica-containing material may also be used as an additional filling material. The hydroxide-catalyzed bonding method forms bonds which are not only as precise and transparent as optical contact bonds, but also as strong and reliable as high-temperature frit bonds. The hydroxide-catalyzed bonding method is also simple and inexpensive.

Gwo, Dz-Hung↗
NASA NTRS2009

Silicon Nanowire Growth at Chosen Positions and Orientations

It is now possible to grow silicon nanowires at chosen positions and orientations by a method that involves a combination of standard microfabrication processes. Because their positions and orientations can be chosen with unprecedented precision, the nanowires can be utilized as integral parts of individually electronically addressable devices in dense arrays. Nanowires made from silicon and perhaps other semiconductors hold substantial promise for integration into highly miniaturized sensors, field-effect transistors, optoelectronic devices, and other electronic devices. Like bulk semiconductors, inorganic semiconducting nanowires are characterized by electronic energy bandgaps that render them suitable as means of modulating or controlling electronic signals through electrostatic gating, in response to incident light, or in response to molecules of interest close to their surfaces. There is now potential for fabricating arrays of uniform, individually electronically addressable nanowires tailored to specific applications. The method involves formation of metal catalytic particles at the desired positions on a substrate, followed by heating the substrate in the presence of silane gas. The figure illustrates an example in which a substrate includes a silicon dioxide surface layer that has been etched into an array of pillars and the catalytic (in this case, gold) particles have been placed on the right-facing sides of the pillars. The catalytic thermal decomposition of the silane to silicon and hydrogen causes silicon columns (the desired nanowires) to grow outward from the originally catalyzed spots on the substrate, carrying the catalytic particles at their tips. Thus, the position and orientation of each silicon nanowire is determined by the position of its originally catalyzed spot on the substrate surface, and the orientation of the nanowire is perpendicular to the substrate surface at the originally catalyzed spot.

Getty, Stephanie A.↗
NASA NTRS2011

The Effect of Photon Source on Heterogeneous Photocatalytic Oxidation of Ethanol by a Silica-Titania Composite

The objective of this study was to distinguish the effect of photon flux (i.e., photons per unit time reaching a surface) from that of photon energy (i.e., wavelength) of a photon source on the silica-titania composite (STC)-catalyzed degradation of ethanol in the gas phase. Experiments were conducted in a bench-scale annular reactor packed with STC pellets and irradiated with either a UV-A fluorescent black light blue lamp ((gamma)max=365 nm) at its maximum light intensity or a UV-C germicidal lamp ((gamma)max=254 nm) at three levels of light intensity. The STC-catalyzed oxidation of ethanol was found to follow zero-order kinetics with respect to CO2 production, regardless of the photon source. Increased photon flux led to increased EtOH removal, mineralization, and oxidation rate accompanied by lower intermediate concentration in the effluent. The oxidation rate was higher in the reactor irradiated by UV-C than by UV-A (38.4 vs. 31.9 nM/s) at the same photon flux, with similar trends for mineralization (53.9 vs. 43.4%) and reaction quantum efficiency (i.e., photonic efficiency, 63.3 vs. 50.1 nmol CO2 (mu)mol/photons). UV-C irradiation also led to decreased intermediate concentration in the effluent . compared to UV-A irradiation. These results demonstrated that STC-catalyzed oxidation is enhanced by both increased photon flux and photon energy.

Coutts, Janelle L.↗
NASA NTRS2011

Possible Increase in Nitric Oxide Production by Lightning Discharges Due to Catalytic Effects of Ice Particles

We address the question of whether ice crystals with habits typically encountered by lightning discharges may serve as catalysts for the production of NOx by lightning. If so, and if the effect is sufficiently large, it would need to be taken into account in estimates of global NOx production by lightning. In this study, we make a series of plausible assumptions about the temperatures and concentrations of reactant species in the environment of discharges and we postulate a mechanism by which ice crystals could adsorb nitrogen atoms. We then compare production rates between uncatalyzed and catalyzed reactions at 2000 K, 3000 K, and 4000 K, temperatures observed in lightning channels during the cool-down period after a return stroke. Catalyzed NO production rates are greater at 2000 K, whereas uncatalyzed production occurs most rapidly at 4000 K. The channel temperature stays around 2000 K for a longer period of time than at 4000 K. The longer residence time at 2000 K is sufficient to allow fresh reactants to participate in the mix in. Therefore, our results suggest that nearly three times as much NO per flash is produced by ice-catalyzed reactions as compared with uncatalyzed reactions.

Peterson, Harold↗
NASA NTRS2013

Trace Contaminant Control: An In-Depth Study of a Silica-Titania Composite for Photocatalytic Remediation of Closed-Environment Habitat Air

This collection of studies focuses on a PCO system for the oxidation of a model compound, ethanol, using an adsorption-enhanced silica-TiO2 composite (STC) as the photocatalyst; studies are aimed at addressing the optimization of various parameters including light source, humidity, temperature, and possible poisoning events for use as part of a system for gaseous trace-contaminant control system in closed-environment habitats. The first goal focused on distinguishing the effect of photon flux (i.e., photons per unit time reaching a surface) from that of photon energy (i.e., wavelength) of a photon source on the PCO of ethanol. Experiments were conducted in a bench-scale annular reactor packed with STC pellets and irradiated with either a UV-A fluorescent black light blue lamp O max=365 nm) at its maximum light intensity or a UV-C germicidal lamp O. max=254 nm) at three levels of light intensity. The STC-catalyzed oxidation of ethanol was found to follow zero-order kinetics with respect to CO2 production, regardless of the photon source. Increased photon flux led to increased EtOH removal, mineralization, and oxidation rate accompanied by lower intermediate concentration in the effluent. The oxidation rate was higher in the reactor irradiated by UV-C than by UV-A (38.4 vs. 31.9 nM s-1 ) at the same photon flux, with similar trends for mineralization (53.9 vs. 43.4%) and reaction quantum efficiency (i.e., photonic efficiency, 63.3 vs. 50.1 nmol C02 ~mol photons-1 ). UV-C irradiation also led to decreased intermediate concentration in the effluent compared to UV -A irradiation. These results demonstrated that STC-catalyzed oxidation is enhanced by both increased photon flux and photon energy. The effect of temperature and relative humidity on the STC-catalyzed degradation of ethanol was also determined using the UV-A light source at its maximum intensity.

Coutts, Janelle L.↗
NASA NTRS2015

A Faster Triphosphorylation Ribozyme

In support of the RNA world hypothesis, previous studies identified trimetaphosphate (Tmp) as a plausible energy source for RNA world organisms. In one of these studies, catalytic RNAs (ribozymes) that catalyze the triphosphorylation of RNA 5'-hydroxyl groups using Tmp were obtained by in vitro selection. One ribozyme (TPR1) was analyzed in more detail. TPR1 catalyzes the triphosphorylation reaction to a rate of 0.013 min -1 under selection conditions (50 mM Tmp, 100 mM MgCl 2 , 22°C). To identify a triphosphorylation ribozyme that catalyzes faster triphosphorylation, and possibly learn about its secondary structure TPR1 was subjected to a doped selection. The resulting ribozyme, TPR1e, contains seven mutations relative to TPR1, displays a previously unidentified duplex that constrains the ribozyme's structure, and reacts at a 24-fold faster rate than the parent ribozyme. Under optimal conditions (150 mM Tmp, 650 mM MgCl 2 , 40°C), the triphosphorylation rate of TRP1e reaches 6.8 min -1 .

Gregory F. Dolan↗
NASA NTRS1980

The assembly and properties of protobiological structures - The beginnings of cellular peptide synthesis

New data indicate that lysine-rich proteinoids have the ability to catalyze the synthesis of peptide bonds from a variety of amino acids and ATP. This capacity is evident in aqueous solution, in suspension of phase-separated complexes of lysine-rich proteinoid with acidic proteinoids, and in suspension of phase-separated particles composed of lysine-rich proteinoids with polynucleotides. Since the proteinoid complexes can contain other catalytic activities, including ability to catalyze internucleotide bond formation, it is inferred that the first protocells on earth already had a number of biological types of activity.

Fox, S. W.↗
NASA NTRS1981

Performance of advanced chromium electrodes for the NASA Redox Energy Storage System

Chromium electrodes were prepared for the NASA Redox Storage System with meet the performance requirements for solar-photovoltaic, wind-turbine and electric utility applications. Gold-lead catalyzed carbon felt electrodes up tp 930 sq cm were fabricated and tested in single cells and multicell stacks for hydrogen evolution, coulombic efficiency, catalyst stability and electrochemical activity. Factors which affect the overall performance of a particular electrode include the carbon felt lot, the cleaning treatment and the gold catalyzation method. Effects of the chromium solution chemistry and impurities on charge/discharge performance are also presented.

Gahn, R. F.↗