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At least 217 records · Page 12

Ceruloplasmin copper induces oxidant damage by a redox process utilizing cell-derived superoxide as reductant

Oxidative damage by transition metals bound to proteins may be an important pathogenic mechanism. Ceruloplasmin (Cp) is a Cu-containing plasma protein thought to be involved in oxidative modification of lipoproteins. We have previously shown that Cp increased cell-mediated low-density lipoprotein (LDL) oxidation by a process requiring cell-derived superoxide, but the underlying chemical mechanism(s) is (are) unknown. We now show that superoxide reduction of Cp Cu is a critical reaction in cellular LDL oxidation. By bathocuproine disulfonate (BCS) binding and by superoxide utilization, we showed that exogenous superoxide reduces a single Cp Cu atom, the same Cu required for LDL oxidation. The Cu atom remained bound to Cp during the redox cycle. Three avenues of evidence showed that vascular cells reduce Cp Cu by a superoxide-dependent process. The 2-fold higher rate of Cp Cu reduction by smooth muscle cells (SMC) compared to endothelial cells (EC) was consistent with their relative rates of superoxide release. Furthermore, Cp Cu reduction by cells was blocked by Cu,Zn superoxide dismutase (SOD1). Finally, the level of superoxide produced by EC and SMC was sufficient to cause the amount of Cu reduction observed. An important role of Cp Cu reduction in LDL oxidation was suggested by results showing that SOD1 inhibited Cp Cu reduction and LDL oxidation by SMC with equal potency, while tumor necrosis factor-alpha stimulated both processes. In summary, these results show that superoxide is a critical cellular reductant of divalent transition metals involved in oxidation, and that protein-bound Cu is a substrate for this reaction. The role of these mechanisms in oxidative processes in vivo has yet to be defined.

NASA Discipline Regulatory Physiology↗

Determination of Meteorite Porosity Using Liquid Nitrogen

We introduce a new harmless method for porosity measurement suitable for meteorite samples. The method is a modification of the traditional Archimedean method based on immersion of the samples in a liquid medium like water or organic liquids. In our case we used liquid nitrogen for its chemically inert characteristics.

Kohout, T.↗

Reactor Parametric Assessments for Alternative Propellant Nuclear Thermal Propulsion Engines

This work focuses on the implications of alternative working fluids for nuclear thermal propulsion (NTP) reactors. To perform this analysis, NASA’s Testing Reference Design (TRD) is altered using parametric studies with selected alternative propellants to determine the reactor modifications required to enable an operable system. This research investigates ammonia, water, methane, helium, and enriched diborane as feasible options to enable a specific impulse (𝐼 𝑠𝑝 ) greater than the chemical propulsion alternatives. Frozen and dissociated 𝐼 𝑠𝑝 for each propellant is shown for variable chamber temperature conditions. Geometrical sensitivities are performed to observe the impact on the neutron multiplication factor (k eff ), system mass, and HALEU loading. Control drum worth curves are included for 5- degree increments of rotation. The base TRD configuration does not enable a critical system for ammonia and enriched diborane, thus these propellants will be highlighted in the final results. Equivalent study results for hydrogen will be included as a point of comparison to the performance of the other options.

Nuclear Thermal Propulsion↗

Chemical Sensors Based on IR Spectroscopy and Surface-Modified Waveguides

Sol-gel processing techniques have been used to apply thin porous films to the surfaces of planar infrared (IR) waveguides to produce widely useful chemical sensors. The thin- film coating serves to diminish the concentration of water and increase the concentration of the analyte in the region probed by the evanescent IR wave. These porous films are composed of silica, and therefore, conventional silica surface modification techniques can be used to give the surface a specific functional character. The sol-gel film was surface-modified to make the film highly hydrophobic. These sensors were shown to be capable of detecting non-polar organic analytes, such as benzonitrile, in aqueous solution with detection limits in the ppb range. Further, these porous sol-gel structures allow the analytes to diffuse into and out of the films rapidly, thus reaching equilibrium in less than ten seconds. These sensors are unique because of the fact that their operation is based on the measurement of an IR absorption spectrum. Thus, these sensors are able to identify the analytes as well as measure concentration with high sensitivity. These developments have been documented in previous reports and publications. Recently, we have also targeted detection of the polar organic molecules acetone and isopropanol in aqueous solution. Polar organics are widely used in industrial and chemical processes, hence it is of interest to monitor their presence in effluents or decontamination process flows. Although large improvements in detection limits were expected with non-polar organic molecules in aqueous solutions using very hydrophobic porous sol-gel films on silicon attenuated total reflectance (Si ATR) waveguides, it was not as clear what the detection enhancements might be for polar organic molecules. This report describes the use of modified sol-gel-coated Si ATR sensors for trace detection and quantitation of small polar organic molecules in aqueous solutions. The detection of both acetone and isopropanol molecules in aqueous solution has been previously reported for chalcogenide fiber optic sensors. The sol-gel film was produced using a mixture of ethyltriethoxysilane and tetraethoxysilane and the surface modification was carried out using trimethylchlorosilane. We have demonstrated that this film concentrates the target polar analytes from aqueous solution in the region probed by the evanescent wave to improve detection limits by as much as a factor of 450.

Lopez, Gabriel P.↗

Spacelab 2 Upper Atmospheric Modification experiment over Arecibo. I - Neutral gas dynamics

The Orbital Maneuvering Subsystem engines of the Space Shuttle were used to inject H2, CO2, H2O and other combustion products into the upper atmosphere over the Arecibo Observatory. Images of the airglow enhancements that resulted from chemical reactions between the exhaust gases and the F-layer plasma showed that the exhaust vapor trail came to rest 80 km downstream from the center of the burn. A computer simulation of the gas dynamics shows that the region of the burn was dominated by a 'snow plow' effect sweeping out a corridor in the atmosphere and collisionally heating the injected vapors.

Bernhardt, P. A.↗

Plasma assisted surface coating/modification processes: An emerging technology

A broad understanding of the numerous ion or plasma assisted surface coating/modification processes is sought. An awareness of the principles of these processes is needed before discussing in detail the ion nitriding technology. On the basis of surface modifications arising from ion or plasma energizing and interactions, it can be broadly classified as deposition of distinct overlay coatings (sputtering-dc, radio frequency, magnetron, reactive; ion plating-diode, triode) and surface property modification without forming a discrete coating (ion implantation, ion beam mixing, laser beam irradiation, ion nitriding, ion carburizing, plasma oxidation). These techniques offer a great flexibility and are capable in tailoring desirable chemical and structural surface properties independent of the bulk properties.

Spalvins, T.↗

Plasma assisted surface coating/modification processes - An emerging technology

A broad understanding of the numerous ion or plasma assisted surface coating/modification processes is sought. An awareness of the principles of these processes is needed before discussing in detail the ion nitriding technology. On the basis of surface modifications arising from ion or plasma energizing and interactions, it can be broadly classified as deposition of distinct overlay coatings (sputtering-dc, radio frequency, magnetron, reactive; ion plating-diode, triode) and surface property modification without forming a discrete coating (ion implantation, ion beam mixing, laser beam irradiation, ion nitriding, ion carburizing, plasma oxidation. These techniques offer a great flexibility and are capable in tailoring desirable chemical and structural surface properties independent of the bulk properties.

Spalvins, T.↗

Computational method to predict thermodynamic, transport, and flow properties for the modified Langley 8-foot high-temperature tunnel

The Langley 8 foot high temperature tunnel (8 ft HTT) is used to test components of hypersonic vehicles for aerothermal loads definition and structural component verification. The test medium of the 8 ft HTT is obtained by burning a mixture of methane and air under high pressure; the combustion products are expanded through an axisymmetric conical contoured nozzle to simulate atmospheric flight at Mach 7. This facility was modified to raise the oxygen content of the test medium to match that of air and to include Mach 4 and Mach 5 capabilities. These modifications will facilitate the testing of hypersonic air breathing propulsion systems for a wide range of flight conditions. A computational method to predict the thermodynamic, transport, and flow properties of the equilibrium chemically reacting oxygen enriched methane-air combustion products was implemented in a computer code. This code calculates the fuel, air, and oxygen mass flow rates and test section flow properties for Mach 7, 5, and 4 nozzle configurations for given combustor and mixer conditions. Salient features of the 8 ft HTT are described, and some of the predicted tunnel operational characteristics are presented in the carpet plots to assist users in preparing test plans.

Venkateswaran, S.↗

Infrared Fiber Optic Sensors

Successive years of Small Business Innovation Research (SBIR) contracts from Langley Research Center to Sensiv Inc., a joint venture between Foster-Miller Inc. and Isorad, Ltd., assisted in the creation of remote fiber optic sensing systems. NASA's SBIR interest in infrared, fiber optic sensor technology was geared to monitoring the curing cycles of advanced composite materials. These funds helped in the fabrication of an infrared, fiber optic sensor to track the molecular vibrational characteristics of a composite part while it is being cured. Foster-Miller ingenuity allowed infrared transmitting optical fibers to combine with Fourier Transform Infrared spectroscopy to enable remote sensing. Sensiv probes operate in the mid-infrared range of the spectrum, although modifications to the instrument also permits its use in the near-infrared region. The Sensiv needle-probe is built to be placed in a liquid or powder and analyze the chemicals in the mixture. Other applications of the probe system include food processing control; combustion control in furnaces; and maintenance problem solving.

Source record↗

Molecular Dynamics Simulations of Adhesion at Epoxy Interfaces

The effect of moisture on adhesives used in aerospace applications can be modeled with chemically specific techniques such as molecular dynamics simulation. In the present study, the surface energy and work of adhesion are calculated for epoxy surfaces and interfaces, respectively, by using molecular dynamics simulation. Modifications are made to current theory to calculate the work of adhesion at the epoxy-epoxy interface with and without water. Quantitative agreement with experimental values is obtained for the surface energy and work of adhesion at the interface without water. The work of adhesion agrees qualitatively with the experimental values for the interface with water: the magnitude is reduced 15% with respect to the value for the interface without water. A variation of 26% in the magnitude is observed depending on the water configuration at a concentration of 1.6 wt%. The methods and modifications to the method that are employed to obtain these values are expected to be applicable for other epoxy adhesives to determine the effects of moisture uptake on their work of adhesion.

Frankland, Sarah-Jane V.↗

Surface Modification at Nanoscale; Nanoparticle-Nanowire Transition

Binary, ternary and quaternary oxides and selenides have been developed and used in multiple applications including high power lasers, detectors, dielectric energy storage and variety of optical devices. These materials have been grown by Bridgman, physical vapor transport (PVT), chemical vapor transport (CVT) methods and flux methods in the form of bulk thin film, nanocrystals and nanowires. With increasing thrust of bio applications, nanoparticles it is essential to understand nucleation and nanomorphological transition during drug delivery, growth of nanoengineered bio composites in body, grain growth and final morphology. Addition of fluorides and selenides have increased significantly in synthetic tissue constituents because of some advantages in adhesion and stability. We have performed experiments on multinary oxides Sr-Ba-O-F, Se-Tl-As and Se-Pb-Sn-Se using several growth methods to demonstrate nanoparticle and nanowire transition. This study has great potential to increase surface area and also provides understanding to the mechanism of nanowire growth.

Singh, N. B.↗

The effect of rocket launches on the ionosphere

A summary is provided of the known theoretical and observational aspects of 'inadvertent' rocket-exhaust effects upon the ionosphere. The atmospheric regions susceptible to rocket exhaust effects are examined. The major perturbations occur in those regions where the sun's radiation causes partial ionization to occur. These regions include the D, E, F1, and F2 regions of the ionosphere. It is found that the dominant cause of atmospheric perturbations due to rocket exhaust rests in the variety of chemical reactions that can occur between the exhaust material (usually molecular species, e.g., H2O, H2, CO2) and the neutral and ionized components of the atmosphere. The observational evidence for artificially-induced ionospheric modifications is discussed and a description is presented of physical processes responsible for ionospheric holes. Attention is given to scientific and technological interest in artificially-created ionospheric holes, and to the large-scale, artificially-induced depletion of the earth's ionosphere which could be monitored in connection with the launch of NASA's third High Energy Astrophysical Observatory.

Mendillo, M.↗

Applying Elastomeric Insulation Inside A Round Case

Elastomer wound onto inside surface in continuous strip. Technique being developed to apply elastomeric insulation to inner surfaces of axisymmetric cases. Requires modification of machine wrapping strip of elastomer on outside of rotating mandrel. Intended for coating insides of rocket-motor cases, technique also used to install elastomeric linings in pressure vessels, containers for chemical, and environmental chambers.

Russell, Peter G.↗

Effect of Space Radiation Processing on Lunar Soil Surface Chemistry: X-Ray Photoelectron Spectroscopy Studies

Current understanding of the chemistry and microstructure of the surfaces of lunar soil grains is dominated by a reference frame derived mainly from electron microscopy observations [e.g. 1,2]. These studies have shown that the outermost 10-100 nm of grain surfaces in mature lunar soil finest fractions have been modified by the combined effects of solar wind exposure, surface deposition of vapors and accretion of impact melt products [1,2]. These processes produce surface-correlated nanophase Feo, host grain amorphization, formation of surface patinas and other complex changes [1,2]. What is less well understood is how these changes are reflected directly at the surface, defined as the outermost 1-5 atomic monolayers, a region not easily chemically characterized by TEM. We are currently employing X-ray Photoelectron Spectroscopy (XPS) to study the surface chemistry of lunar soil samples that have been previously studied by TEM. This work includes modification of the grain surfaces by in situ irradiation with ions at solar wind energies to better understand how irradiated surfaces in lunar grains change their chemistry once exposed to ambient conditions on earth.

Dukes, C.↗

Strategies for Stabilizing Nitrogenous Compounds in ECLSS Wastewater: Top-Down System Design and Unit Operation Selection with Focus on Bio-Regenerative Processes for Short and Long Term Scenarios

Water recycling and eventual nutrient recovery is crucial for surviving in or past low earth orbit. New approaches and syste.m architecture considerations need to be addressed to meet current and future system requirements. This paper proposes a flexible system architecture that breaks down pretreatment , steps into discrete areas where multiple unit operations can be considered. An overview focusing on the urea and ammonia conversion steps allows an analysis on each process's strengths and weaknesses and synergy with upstream and downstream processing. Process technologies to be covered include chemical pretreatment, biological urea hydrolysis, chemical urea hydrolysis, combined nitrification-denitrification, nitrate nitrification, anammox denitrification, and regenerative ammonia absorption through struvite formation. Biological processes are considered mainly for their ability to both maximize water recovery and to produce nutrients for future plant systems. Unit operations can be considered for traditional equivalent system mass requirements in the near term or what they can provide downstream in the form of usable chemicals or nutrients for the long term closed-loop ecological control and life support system. Optimally this would allow a system to meet the former but to support the latter without major modification.

Lunn, Griffin M.↗

Improved Anode for a Direct Methanol Fuel Cell

A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the catalyst by increasing electrical connectivity between catalyst particles. However, the relatively low density of carbon results in thick catalyst layers that impede the mass transport of methanol to the catalytic sites. Also, the electrical conductivity of carbon is less than 1/300th of typical metals. Furthermore, the polymer-electrolyte membrane material is acidic and most metals are not chemically stable in contact with it. Finally, a material that conducts electrons (but not protons) does not contribute to the needed transport of protons produced in the electro-oxidation reaction.

Valdez, Thomas↗

Processing modifications for improved propellants - Coated oxidizers

The present investigation is concerned with a technique which makes it possible to improve greatly the performance of composite propellants by alleviating the combustion instability problem. The technique involves the coating of the oxidizer crystals (typically ammonium perchlorate) with a suitably selected chemical. For each application the chemical for the coating is chosen on the basis of a screening procedure including the employment of differential scanning calorimetry and the use of a thermogravimetric analyzer. It is particularly important that the coat chemicals have good thermochemical stability at temperatures up to the normal surface temperature of the propellant during time-independent combustion (typically 800 to 900 K). At higher temperatures, sudden degradation should occur over a vary narrow temperature range (10-20 C).

Helmy, A. K.↗

Fine-Grained Rims in the Allan Hills 81002 and Lewis Cliff 90500 CM2 Meteorites: Their Origin and Modification

Antarctic CM meteorites Allan Hills (ALH) 8 1002 and Lewis Cliff (LEW) 90500 contain abundant fine-grained rims (FGRs) that surround a variety of coarse-grained objects. FGRs from both meteorites have similar compositions and petrographic features, independent of their enclosed objects. The FGRs are chemically homogeneous at the 10 m scale for major and minor elements and at the 25 m scale for trace elements. They display accretionary features and contain large amounts of volatiles, presumably water. They are depleted in Ca, Mn, and S but enriched in P. All FGRs show a slightly fractionated rare earth element (REE) pattern, with enrichments of Gd and Yb and depletion of Er. Gd is twice as abundant as Er. Our results indicate that those FGRs are not genetically related to their enclosed cores. They were sampled from a reservoir of homogeneously mixed dust, prior to accretion to their parent body. The rim materials subsequently experienced aqueous alteration under identical conditions. Based on their mineral, textural, and especially chemical similarities, we conclude that ALH 8 1002 and LEW 90500 likely have a similar or identical source.

Hua, X.↗