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At least 253 records · Page 14

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NASA NTRS1996

Southern Hemisphere In Situ Observations of OH, HO2, CIO and BrO from the ER-2 Aircraft for the 1994 ASHOE Mission

A summary of the first order scientific conclusions that emerged from the research done under this grant are as follows: (1) For the first time, the concentration of the key hydrogen and halogen radicals OH, H02, ClO and BrO were determined on a global scale extending from the arctic circle to the antarctic circle, over the altitude domain of the ER-2. That domain extends from 15-20 km altitude, covering a critical part of the lower stratosphere; (2) Simultaneous, in situ measurements of the concentrations of OH, H02, ClO, BrO, NO and NO2 demonstrate the predominance of odd-hydrogen and halogen free radical catalysis in determining the rate of removal of ozone in the lower stratosphere over the complete ASHOE mission. This extends to the global scale the "first look" data obtained during the NASA Stratospheric Photochemistry and Dynamics Experiment (SPADE), executed out of Ames Research Center in June 1993. This represents a major rearrangement of our understanding with respect to the hierarchy of dominant catalytic cycles controlling ozone loss in the lower stratosphere. For the past twenty years, it has been assumed that nitrogen radicals dominate the destruction rate of ozone in the lower stratosphere; (3) Throughout the altitude and latitude range covered by ASHOE, it was determined that a single catalytic cycle, HO2 + O3 yields OH + 2O2, accounted for one half of the total O3 removal in this region of the atmosphere. Halogen radical catalytic cycles were found to account for one third of the ozone loss, and nitrogen radicals were found to account for 20% of the loss; (4) Simultaneous observations of the full complement of radicals, tracers, ozone, and water vapor during ASHOE demonstrated quantitatively the coupling that exists between the rate limiting radicals and other reactive species in the photochemical reaction network. Specifically, the concentrations of ClO and HO2 are inversely correlated with the concentration of NOx. This carries the implication that the NOx effluent from the proposed High Speed Civil Transport may be less destructive to stratospheric ozone than had previously been thought. ASHOE brought this conclusion forward for the first time on a global basis; and (5) The density of BrO was measured on a global scale during ASHOE in the lower stratosphere. It was found that bromine is responsible for 55-65% of the local rate of catalytic destruction of ozone by reactions involving bromine and chlorine. Normalizing calculated loss rates to total available inorganic bromine and chlorine explicitly demonstrates that bromine is 60-80 times more efficient than chlorine in removing ozone in the lower stratosphere. An inferred value of total inorganic bromine is in excellent agreement with measurements of their source species, organic bromine compounds in the troposphere.

Anderson, James G.↗

NASA NTRS1997

[Ribosomal RNA Evolution]

It is generally believed that an RNA World existed at an early stage in the history of life. During this early period, RNA molecules are seen to be potentially involved in both catalysis and the storage of genetic information. Translation presents several interrelated themes of inquiry for exobiology. First, it is essential, for understanding the very origin of life, how peptides and eventually proteins might have come to be made on the early Earth in a template directed manner. Second, it is necessary to understand how a machinery of similar complexity to that found in the ribosomes of modern organisms came to exist by the time of the last common ancestor (as detected by 16S rRNA sequence studies). Third, the ribosomal RNAs themselves likely had a very early origin and studies of their history may be very informative about the nature of the RNA World. Moreover, studies of these RNAs will contribute to a better understanding of the potential roles of RNA in early evolution.During the past year we have ave conducted a comparative study of four completely sequenced bacterial genoames. We have focused initially on conservation of gene order. The second component of the project continues to build on the model system for studying the validity of variant 5S rRNA sequences in the vicinity of the modern Vibrio proteolyticus 5S rRNA that we established earlier. This system has made it possible to conduct a detailed and extensive analysis of a local portion of the sequence space. These core methods have been used to construct numerous mutants during the last several years. Although it has been a secondary focus, this work has continued over the last year such that we now have in excess of 125 V. proteolyticus derived constructs which have been made and characterized. We have also continued high resolution NMR work on RNA oligomers originally initiated by G. Kenneth Smith who was funded by a NASA Graduate Student Researcher's Fellowship Award until May of 1996. Mr. Smith developed synthesis & purification protocols in order to obtain large quantities of RNA oligomers for NMR studies. He succeeded in obtaining preliminary one dimensional spectra for an analog of the helix II/loop B/helix III domain of 5S rRNAs well as a 29mer which includes helix III and the highly characteristic 13 nucleotide loop C. Significant progress in laying the required groundwork for this work has been accomplished during the past year. A plasmid, pLeuS-1, carrying the E. coli leucine tRNA synthetase gene (LeuRS) has been obtained and used to overexpressed the leucine synthetase. A T7 runoff transcription has been established in our laboratory and successfully used to make both minihelix RNAs and tRNAs. In addition, encapsulation studies have been conducted and we have successfully encapsulated tRNA in lipid vesicles. Initial efforts to obtain peptide bond synthesis will be underway over the next several moths.

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NASA NTRS1985

Design and Performance Analysis of a Conical Aerobrake Orbital Transfer Vehicle Concept

A Shuttle-compatible systems design based on the core concept of attachable modules for the major vehicle components is proposed. The principal features include a disposable cargo/extra-propellant tank module; a porous, radiative, back-scattering drag-brake surface material of thin silica cloth; and a lightweight carbon-composite support structure. The mission payload capability for delivery, retrieval, and combined operations is determined for a broad range of missions including NASA/DOD requirements and extending through cislunar space. The effects of finite-rate surface catalysis, negative lift, and multiple atmospheric passes in reducing the aerothermodynamic heating rates are also investigated. In addition, the structural and thermal protection problems of the drag-brake support apparatus are analyzed, and recommendations are proposed for future design refinements.

Menees, Gene P.↗

NASA NTRS1997

Surface Plasmon Resonance Evaluation of Colloidal Metal Aerogel Filters

We have fabricated aerogels containing gold, silver, and platinum nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Smith, David D.↗

NASA NTRS1998

Noble Metal Immersion Spectroscopy of Silica Alcogels and Aerogels

We have fabricated aerogels containing gold and silver nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Smith, David D.↗

NASA NTRS2000

Cryo-Trapping the Distorted Octahedral Reaction Intermediate of Manganese Superoxide Dismutase

Superoxide dismutase protects organisms from potentially damaging oxygen radicals by catalyzing the disproportion of superoxide to oxygen and hydrogen peroxide. We report the use of cryogenic temperatures to kinetically trap the 6th ligand bound to the active site of manganese superoxide dismutase. Using cryocrystallography and synchrotron radiation, we describe at 1.55A resolution the six-coordinate, distorted octahedral geometry assumed by the active site during catalysis and compare it to the room temperature, five-coordinate trigonal-bipyramidal active site. Gateway residues Tyr34, His30 and a tightly bound water molecule are implicated in closing off the active site and blocking the escape route of superoxide during dismutation.

Borgstahl, Gloria↗

NASA NTRS2000

Cryo-Trapping the Distorted Octahedral Reaction Intermediate of Manganese Superoxide Dismutase

Borgstahl, Gloria↗

NASA NTRS2001

Characterization of Carbon Nanotubes Grown by Chemical Vapor Deposition

Since the superior properties of multi-wall carbon nanotubes (MWCNT) could improve numerous devices such as electronics and sensors, many efforts have been made in investigating the growth mechanism of MWCNT to synthesize high quality MWCNT. Chemical vapor deposition (CVD) is widely used for MWCNT synthesis, and scanning electron microscopy (SEM) and energy dispersive x-ray spectroscopy (EDS) are useful methods for analyzing the structure, morphology and composition of MWCNT. Temperature and pressure are two important growth parameters for fabricating carbon nanotubes. In MWCNT growth by CVD, the plasma assisted method is normally used for low temperature growth. However a high temperature environment is required for thermal CVD. A systematic study of temperature and pressure-dependence is very helpful to understanding MWCNT growth. Transition metal particles are commonly used as catalysis in carbon nanotube growth. It is also interesting to know how temperature and pressure affect the interface of carbon species and catalyst particles

Cochrane, J. C.↗

NASA NTRS2001

Mechanisms for Midlatitude Ozone Loss: Heterogeneous Chemistry in the Lowermost Stratosphere?

The question of midlatitude ozone erosion by chlorine free radical catalysis is examined. We present and analyze simultaneous, high-resolution observations of ClO, H2O, tropopause height, particle reactive surface area, and ice saturation occurrence frequency obtained from the NASA ER-2 aircraft. The objective is to test the hypothesis that the existence of cirrus clouds or cold aerosols in the first few kilometers above the tropopause at midlatitudes is responsible for increasing the ratio of chlorine free radicals to total inorganic chlorine, thus amplifying the rate of catalytic ozone destruction. The observations reveal a sharp decrease in ice saturation frequency at the tropopause, a marked degree of undersaturation just above the tropopause, a corresponding sharp gradient in the product of cold aerosol reactive surface area and reaction probability, gamma-S(sub a), and, finally, the consistent absence of enhanced concentrations of ClO immediately above the tropopause. These results suggest that midlatitude ozone loss is not controlled in situ by the mechanism of cirrus cloud and/or cold aerosol enhancement of chlorine radicals in the vicinity of the tropopause.

Smith, Jessica B.↗

NASA NTRS2001

Flame Synthesis of Single- and Multi-Walled Carbon Nanotubes and Nanofibers

Metal-catalyzed carbon nanotubes are highly sought for a diverse range of applications that include nanoelectronics, battery electrode material, catalysis, hydrogen storage media and reinforcing agents in polymer composites. These latter applications will require vast quantities of nanotubes at competitive prices to be economically feasible. Moreover, reinforcing applications may not require ultrahigh purity nanotubes. Indeed, functionalization of nanotubes to facilitate interfacial bonding within composites will naturally introduce defects into the tube walls, lessening their tensile strength. Current methods of aerosol synthesis of carbon nanotubes include laser ablation of composite targets of carbon and catalyst metal within high temperature furnaces and decomposition of a organometallics in hydrocarbons mixtures within a tube furnace. Common to each approach is the generation of particles in the presence of the reactive hydrocarbon species at elevated temperatures. In the laser-ablation approach, the situation is even more dynamic in that particles and nanotubes are borne during the transient cooling phase of the laser-induced plasma for which the temperature far exceeds that of the surrounding hot gases within the furnace process tube. A shared limitation is that more efficient methods of nanoparticle synthesis are not readily incorporated into these approaches. In contrast, combustion can quite naturally create nanomaterials such as carbon black. Flame synthesis is well known for its commercial scalability and energy efficiency. However, flames do present a complex chemical environment with steep gradients in temperature and species concentrations. Moreover, reaction times are limited within buoyant driven flows to tens of milliseconds. Therein microgravity can greatly lessen temperature and spatial gradients while allowing independent control of flame residence times. In preparation for defining the microgravity experiments, the work presented here focuses on the effect of catalyst particle size and reactant gas in 1g.

VanderWal, R. L.↗

NASA NTRS2000

Extraterrestrial Organic Chemistry: From the Interstellar Medium to the Origins of Life

Extraterrestrially delivered organics in the origin of cellular life. Various processes leading to the emergence of cellular life from organics delivered from space to earth or other planetary bodies in the solar system will be reviewed. The focus will be on: (1) self-assembly of amphiphilic material to vesicles and other structures, such as micelles and multilayers, and its role in creating environments suitable for chemical catalysis, (2) a possible role of extraterrestrial delivery of organics in the formation of the simplest bioenergetics (3) mechanisms leading from amino acids or their precursors to simple peptides and, subsequently, to the evolution of metabolism. These issues will be discussed from two opposite points of view: (1) Which molecules could have been particularly useful in the protobiological evolution; this may provide focus for searching for these molecules in interstellar media. (2) Assuming that a considerable part of the inventory of organic matter on the early earth was delivered extraterrestrially, what does relative abundance of different organics in space tell us about the scenario leading to the origin of life.

Pohorille, Andrew↗

NASA NTRS2000

The Decomposition of Carbonates and Organics on Mars

The return and analysis of pristine material that is relict of a putative period of chemical evolution is a fumdamental goal of the exobiological exploration of Mars. In order to accomplish this objective, it is desirable to find oxidant-free regions where pristine material can be accessed at the shallowest possible depth (ideally directly from the surface). The objective of our ongoing research is to understand the spatial and temporal distribution of oxidants in the martian regolith and the redox chemistry of the soil; in effect to understand the chemical mechanisms and kinetics relating to the in-situ destruction of organics and the formation of the reactive species responsible for the Viking biology results. In this work, we report on experimental studies of oxidizing processes that may contribute to carbonate and organic degradation on Mars. Organic molecules directly exposed to solar UV may decomposed either directly into CO2, or into more volatile organic fragments. Organic macromolecules not directly exposed to high UV flux are most likely to be affected by atmospheric oxidants which can diffuse to their surfaces. The oxidizing processes examined include: gas-phase oxidants, UV photolysis, and UV-assisted heterogeneous catalysis. For example, assuming a meteroritic infall rate of 4 x 10(exp -4) g/m^2yr (Flynn and McKay 1990) and a flux of organic carbon of 2 x 10(exp -5) g/m^2yr, laboratory measurements of the UV-assisted decomposition of benzenehexacarboxylic acid (mellitic acid, a likely intermediate of kerogen oxidation), indicate its decomposition rate on Mars would exceed the total flux of organic carbon to the planet by over four orders of magnitude. Our measurements indicate that although the decomposition temperature of kerogens in some cases exceeds the temperature limit of the Viking GCMS, it is unlikely kerogens or their decomposition intermediates were present at the Viking landings sites at levels above the GCMS detection limits.

Quinn, Richard C.↗

NASA NTRS2001

Molecular Dynamics Studies of Structure and Functions of Water-Membrane Interfaces

A large number of essential cellular processes occur at the interfaces between water and membranes. The selectivity and dynamics of these processes are largely determined by the structural and electrical properties of the water-membrane interface. We investigate these properties by the molecular dynamics method. Over the time scales of the simulations, the membrane undergoes fluctuations described by the capillary wave model. These fluctuations produce occasional thinning defects in the membrane which provide effective pathways for passive transport of ions and small molecules across the membrane. Ions moving through the membrane markedly disrupt its structure and allow for significant water penetration into the membrane interior. Selectivity of transport, with respect to ionic charge, is determined by the interfacial electrostatic potential. Many small molecules. of potential significance in catalysis, bioenergetics and pharmacology, are shown to bind to the interface. The energetics and dynamics of this process will be discussed.

Pohorille, Andrew↗

NASA NTRS1999

Aerogel Materials by Evaporative Drying: Potential for Space Applications

Aerogel wafers were made using an evaporative drying procedure. The main steps were sol formulation, gelation, aging, capping, and drying. Of these, the most critical step was drying. Both the rate of evaporation and temperature of the system must be controlled for best results. Aerogel materials should be benchmarked against more traditional foams and current systems may have to be redesigned to make best use of aerogel strengths. Finally, the flexibility of this procedure lends itself to producing aerogel materials for many uses other than insulation. Such uses may include catalysis, sensing, and composite materials.

Plawsky, Joel L.↗

NASA NTRS2002

Structural Studies of Human Pyruvate Dehydrogenase

Human pyruvate dehydrogenase (E1) catalyzes the irreversible decarboxylation of pyruvate in the presence of Mg(2+) and thiamin pyrophosphate (TPP) followed by the rate-limiting reductive acetylation of the lipoyl moiety linked to dihydrolipoamide acetyltransferase. The three-dimensional structure of human E1 is elucidated using the methods of macromolecular X-ray crystallography. The structure is an alpha, alpha', beta and beta' tetramer with the protein units being in the tetrahedral arrangement. Each 361-residue alpha-subunit and 329-residue beta-subunit is composed of a beta-sheet core surrounded by alpha-helical domains. Each subunit is in extensive contact with all the three subunits involving TPP and magnesium cofactors, and potassium ions. The two binding sites for TPP are at the alpha-beta' and alpha'-beta interfaces, each involving a magnesium ion and Phe6l, His63, Tyr89, and Met200 from the alpha-subunit (or alpha'-subunit), and Met81 Phe85, His128 from the beta-subunit (or beta'-subunit). K+ ions are nestled between two beta-sheets and the end of an alpha-helix in each beta-subunit, where they are coordinated by four carbonyl oxygen groups from Ile12, Ala160, Asp163, and Asnl65, and a water molecule. The catalytic C2 carbon of thiazolium ring in this structure forms a 3.2 A contact with a water molecule involved in a series of H-bonds with other water molecules, and indirectly with amino acids including those involved in the catalysis and regulation of the enzyme.

Ciszak, Ewa↗

NASA NTRS1992

Water Purification Systems

A water purification/recycling system developed by Photo-Catalytics, Inc. (PCI) for NASA is commercially available. The system cleanses and recycles water, using a "photo-catalysis" process in which light or radiant energy sparks a chemical reaction. Chemically stable semiconductor powders are added to organically polluted water. The powder absorbs ultraviolet light, and pollutants are oxidized and converted to carbon dioxide. Potential markets for the system include research and pharmaceutical manufacturing applications, as well as microchip manufacture and wastewater cleansing.

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NASA NTRS2003

Catalyzed Ignition of Bipropellants in Microtubes

This paper addresses the need to understand the physics and chemistry involved in propellant combustion processes in micro-scale combustors for propulsion systems on micro-spacecraft. These spacecraft are planned to have a mass less than 50 kilograms with attitude control estimated to be in the 10 milli-Newton thrust class. These combustors are anticipated to be manufactured using Micro Electrical Mechanical Systems (MEMS) technology and are expected to have diameters approaching the quenching diameter of the propellants. Combustors of this size are expected to benefit significantly from surface catalysis processes. Miniature flame tube apparatus is chosen for this study because microtubes can be easily fabricated from known catalyst materials and their simplicity in geometry can be used in fundamental simulations to more carefully characterize the measured heat transfer and pressure losses for validation purposes. Experimentally, we investigate the role of catalytically active surfaces within 0.4 and 0.8 mm internal diameter micro-tubes, with special emphases on ignition and extinction processes in fuel rich gaseous hydrogen and gaseous oxygen. Flame thickness and reaction zone thickness calculations predict that the diameters of our test apparatus are below the quenching diameter of the propellants in sub-atmospheric tests. Temperature and pressure rises in resistively heated platinum and palladium micro-tubes are used as an indication of exothermic reactions. Specific data on mass flow versus preheat temperature required to achieve ignition are presented.

Schneider, Steven J.↗

NASA NTRS2003

Evolution of Local Microstructures: Spatial and Temporal Correlation in Clusters Undergoing 2-Dimensional Diffusion

Diffusion-limited, capillarity-driven, coarsening of precipitates is an important and intensively studied phenomenon. Coarsening can occur among several microstructural constituents ranging from the primary phases to widely dispersed precipitates. Moreover, coarsening of three-dimensional (3-D) phase domains, occurring via mass transport through a two-dimensional (2-D) diffusion field (called mixed-dimensional phase coarsening) is a cooperative phenomenon that is of practical importance, especially in thin film technologies and catalysis. A primary objective of our current work is to focus on the details of evolving microstructures through a study of 'island' formation in heteroepitaxial film/substrate systems. Whereas this work has been designed for space-based coarsening studies, which require long-duration quality microgravity to observe 3-D Ostwald ripening, a significant amount of work has been performed during ground-based studies to observe diffusional coarsening in a liquid-liquid two-phase system. We have performed the experiment at an isopycnic point to maximize exclusion of gravity-based system disturbance. This has allowed observations of 3-D droplets, immobilized by container wall contact, undergoing coarsening by 2-D diffusion for the required long times (approximately 4 months) using a holographic imaging technique. Although such systems may not be as reliant on long-duration microgravity processing as 3-D systems are, they are of direct relevance to so-called mixed-dimensional coarsening and to the study of heterostructures grown by thin-film technique

Curreri, Peter A.↗