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At least 109 records · Page 6

Ceruloplasmin and cardiovascular disease

Transition metal ion-mediated oxidation is a commonly used model system for studies of the chemical, structural, and functional modifications of low-density lipoprotein (LDL). The physiological relevance of studies using free metal ions is unclear and has led to an exploration of free metal ion-independent mechanisms of oxidation. We and others have investigated the role of human ceruloplasmin (Cp) in oxidative processes because it the principal copper-containing protein in serum. There is an abundance of epidemiological data that suggests that serum Cp may be an important risk factor predicting myocardial infarction and cardiovascular disease. Biochemical studies have shown that Cp is a potent catalyst of LDL oxidation in vitro. The pro-oxidant activity of Cp requires an intact structure, and a single copper atom at the surface of the protein, near His(426), is required for LDL oxidation. Under conditions where inhibitory protein (such as albumin) is present, LDL oxidation by Cp is optimal in the presence of superoxide, which reduces the surface copper atom of Cp. Cultured vascular endothelial and smooth muscle cells also oxidize LDL in the presence of Cp. Superoxide release by these cells is a critical factor regulating the rate of oxidation. Cultured monocytic cells, when activated by zymosan, can oxidize LDL, but these cells are unique in their secretion of Cp. Inhibitor studies using Cp-specific antibodies and antisense oligonucleotides show that Cp is a major contributor to LDL oxidation by these cells. The role of Cp in lipoprotein oxidation and atherosclerotic lesion progression in vivo has not been directly assessed and is an important area for future studies.

NASA Discipline Cell Biology↗

Applications of artificial intelligence for chemical inference. V.

Discussion of the modification of the DENDRAL computer program to extend the program to cyclic structures which exceed numerically the linear molecules of a given composition. IR, NMR and mass spectroscopy is used to develop a method for identification of each of the 27 possible ketones (exclusive of 5 cyclopropanones) of composition C6H10O.

Sheikh, Y. M.↗

Field-aligned dynamics of chemically induced perturbations to the ionosphere

Ionospheric modification using photochemically reactive vapors is studied with a one-dimensional, multiion, fluid model of plasma flow along magnetic field lines. The magnitudes of ion and electron density changes are determined by considering both chemical processes (i.e., photoionization, ion-molecule reactions, dissociative recombination, electron attachment) and transport processes (i.e., multispecies diffusion, electric currents, ambipolar electric fields). The numerical treatment in the model is not specific to any type of release or any interaction chemistry. It has been used to simulate releases of Ba, CO2, and CF3Br in the ionosphere, but generalization to other species may be easily accomplished. The results of the calculations are found to be in good agreement with experimental observations. The feasibility of modifying the parallel current paths in the auroral F region is examined.

Bernhardt, P. A.↗

The Addition of EI/CI Capability to the Mattauch-herzog Spectrograph with EOID

A modification was made to the Mattauch-Herzog Spectrograph with an electro-optical ion detector (EOID) previously designed and constructed, so that it would be capable of operating not only in the electron-impact (EI) mode of ionization, but also in the chemical ionization (CI) mode. This modification necessitated an effort in three specific design areas: (1) sample inlet; (2) ion source and analyzer regions; and (3) the pumping system. In addition, an appropriate electronics package had to be designed to control and operate the combined EI/CI source.

Fergusson, G. J.↗

The nakhlite meteorites: Augite-rich igneous rocks from Mars

The seven nakhlite meteorites are augite-rich igneous rocks that formed in flows or shallow intrusions of basaltic magma on Mars. They consist of euhedral to subhedral crystals of augite and olivine (to 1 cm long) in fine-grained mesostases. The augite crystals have homogeneous cores of Mg' = 63% and rims that are normally zoned to iron enrichment. The core-rim zoning is cut by iron-enriched zones along fractures and is replaced locally by ferroan low-Ca pyroxene. The core compositions of the olivines vary inversely with the steepness of their rim zoning - sharp rim zoning goes with the most magnesian cores (Mg' = 42%), homogeneous olivines are the most ferroan. The olivine and augite crystals contain multiphase inclusions representing trapped magma. Among the olivine and augite crystals is mesostasis, composed principally of plagioclase and/or glass, with euhedra of titanomagnetite and many minor minerals. Olivine and mesostasis glass are partially replaced by veinlets and patches of iddingsite, a mixture of smectite clays, iron oxy-hydroxides and carbonate minerals. In the mesostasis are rare patches of a salt alteration assemblage: halite, siderite, and anhydrite/ gypsum. The nakhlites are little shocked, but have been affected chemically and biologically by their residence on Earth. Differences among the chemical compositions of the nakhlites can be ascribed mostly to different proportions of augite, olivine, and mesostasis. Compared to common basalts, they are rich in Ca, strongly depleted in Al, and enriched in magmaphile (incompatible) elements, including the LREE. Nakhlites contain little pre-terrestrial organic matter. Oxygen isotope ratios are not terrestrial, and are different in anhydrous silicates and in iddingsite. The alteration assemblages all have heavy oxygen and heavy carbon, while D/H values are extreme and scattered. Igneous sulfur had a solar-system isotopic ratio, but in most minerals was altered to higher and lower values. High precision analyses show mass-independent fractionations of S isotopes. Nitrogen and noble gases are complex and represent three components: two mantle sources (Chas-E and Chas-S), and fractionated Martian atmosphere. The nakhlites are igneous cumulate rocks, formed from basaltic magma at approx.1.3 Ga, containing excess crystals over what would form from pure magma. After accumulation of their augite and olivine crystals, they were affected (to various degrees) by crystallization of the magma, element diffusion among minerals and magma, chemical reactions among minerals and magma, magma movement among the crystals, and post-igneous chemical equilibration. The extent of these modifications varies, from least to greatest, in the order: MIL03346, NWA817, Y000593, Nakhla = Governador Valadares, Lafayette, and NWA998. Chemical, isotopic, and chronologic data confirm that the nakhlites formed on Mars, most likely in thick lava flows or shallow intrusions. Their crystallization ages, referenced to crater count chronologies for Mars, suggest that the nakhlites formed on the large volcanic constructs of Tharsis, Elysium, or Syrtis Major. The nakhlites were suffused with liquid water, probably at approx.620 ma. This water dissolved olivine and mesostasis glass, and deposited iddingsite and salt minerals in their places. The nakhlites were ejected from Mars at approx.10.75Ma by an asteroid impact and fell to Earth within the last 10,000 years. Although the nakhlites are enriched in incompatible elements, their source mantle was strongly depleted. This depletion event was ancient, as the nakhlites source mantle was fractionated while short-lived radionuclides (e.g., t(sub 1/2 = 9 my) were still active. This differentiation event may have been core formation coupled with a magma ocean, as is inferred for the moon.

Treiman, Allan H.↗

The Space Station neutral gas environment and the concomitant requirements for monitoring

At 340 km, for typical conditions, the neutral atmospheric density is several times 10E8/cc and is thus more abundant than the ionized component by several factors of 10. At that altitude, the principal series is atomic oxygen with 10 percent N2, and 1 percent He, and trace amounts of O2, H, N, NO, and Ar. The constituent densities are highly variable with local time, latitude, and geophysical indices. The physical interaction with surfaces at orbital velocity leads to large buildup of density on forward faces and great depletions in the wakes of objects. Chemical reactions lead to major modifications in constituent densities as in the case of the conversion of most colliding oxygen atoms to oxygen bearing molecules. The neutral environment about an orbiting body is thus a complex product of many variables even without a source of neutral contaminants. The addition of fluxes of gases emanating from the orbiting vehicle, as will be the case for the Space Station, with the associated physical and chemical interactions adds another level of complexity to the character of the environment and mandates a sophisticated measurement capability if the neutral environment is to be quantitatively characterized.

Carignan, George↗

Lunar Dust Simulant Particle Adhesion on Copolyimide Alkyl Ethers

Mitigation of lunar dust contamination is one of the greatest challenges to be overcome to realize a sustained lunar presence. Likely solutions will integrate active mitigation strategies, requiring the input of external energy, and passive materials, exhibiting an intrinsic resistance to lunar dust adhesion. In this work, a series of copolyimide alkyl ethers containing per fluorinated side-chains were generated to evaluate the influence surface modification agents have on surface chemical, topographical, and mechanical properties. An expanded testing protocol to characterize the adhesion interaction between lunar dust simulant and the copolyimide substrate was carried out. The interfacial adhesion strength was in-situ measured by a custom-built particulate adhesion instrument, utilizing a sonic wand. Surface mechanical properties were characterized by nanoindentation, utilizing the continuous stiffness measurement approach. A nominal presence of surface modifying agents, 1 wt%, resulted in a six-fold reduction in adhesion strength of the interface. A strong inverse correlation between the adhesion strength and Young’s modulus of the substrate was identified. The reduction was attributed to a synergistic interaction between the surface energy, surface roughness, and modulus of the copolyimide alkyl ethers film.

Lunar Dust, Particulate Adhesion, Surface Migratio↗

Source term evaluation for combustion modeling

A modification is developed for application to the source terms used in combustion modeling. The modification accounts for the error of the finite difference scheme in regions where chain-branching chemical reactions produce exponential growth of species densities. The modification is first applied to a one-dimensional scalar model problem. It is then generalized to multiple chemical species, and used in quasi-one-dimensional computations of shock-induced combustion in a channel. Grid refinement studies demonstrate the improved accuracy of the method using this modification. The algorithm is applied in two spatial dimensions and used in simulations of steady and unsteady shock-induced combustion. Comparisons with ballistic range experiments give confidence in the numerical technique and the 9-species hydrogen-air chemistry model.

Sussman, Myles A.↗

Organic Modification of a Layered Silicate by Co-Ion Exchange of an Alkyl Ammonium and a Mono-Protonated Diamine

Co-Ion exchange of the interlayer cations of a layered silicate with a mono-protonated aromatic diamine and an alkyl ammonium ion into the silicate galleries. The presence of the alkyl ammonium ion provides low oligomer melt viscosity during processing. The presence of the diamine allows chemical reaction between the silicate surface modification and the monomers. This reaction strengthens the polymer silicate interface, and ensures irreversible separation of the individual silicate layers. Improved polymer thermal oxidative stability and mechanical properties are obtained.

Sandi G Campbell↗

Studies of silicon pn junction solar cells

Modifications of the basic Shockley equations that result from the random and nonrandom spatial variations of the chemical composition of a semiconductor were developed. These modifications underlie the existence of the extensive emitter recombination current that limits the voltage over the open circuit of solar cells. The measurement of parameters, series resistance and the base diffusion length is discussed. Two methods are presented for establishing the energy bandgap narrowing in the heavily-doped emitter region. Corrections that can be important in the application of one of these methods to small test cells are examined. Oxide-charge-induced high-low-junction emitter (OCI-HLE) test cells which exhibit considerably higher voltage over the open circuit than was previously seen in n-on-p solar cells are described.

Lindholm, F. A.↗

Thermal Modification of Silicate Materials on Flash-heated Sulfide IDPs: The First Clues for Chemically Controlled, Early Silicate Mineral Evolution

Variable Ca-compositions of flash heated ferromagnesiosilica materials on massive sulfide IDPs provide the first clues for chemically controlled nucleation of pyroxenes during the earliest stages of silicate mineral evolution in solar nebula dust. Additional information is contained in the original extended abstract.

Rietmeijer, F. J. M.↗

Origins of outer-planet satellites

Aspects of satellite origin and evolution which bear on the formation of the solar system are addressed, with emphasis on the chemical evidence contained in satellites concerning the modification of the interstellar material which went to form the solar system. New results on the tidal evolution of outer-planet satellite systems are presented. The gross physical and chemical properties of the satellite systems of the outer planets are outlined. Models for regular satellite formation are reviewed. Attention is given to the evolution of the satellites, with emphasis on tidal evolution, including a discussion of the dynamical origin of Triton. The volatile budgets of Titan, Triton, and Pluto/Charon are discussed, and models are presented for the origin of these budgets which tie them to the larger set of processes associated with solar system formation.

Lunine, Jonathan I.↗

Suppressants for lowering propellant binder burning rate

Addition of boron compound to lower burning rate of solid propellant binder is reported. Chemical reactions involved in propellant binder modification are described. Advantages of method for lowering burning rate are analyzed.

Thompson, W. W.↗

Overview of NASA FINESSE (Field Investigations to Enable Solar System Science and Exploration) Science and Exploration Results

NASA's FINESSE (Field Investigations to Enable Solar System Science and Exploration) project is focused on a science and exploration field-based research program to generate strategic knowledge in preparation for human and robotic exploration of other planetary bodies including our moon, Mars' moons Phobos and Deimos, and near-Earth asteroids. Scientific study focuses on planetary volcanism (e.g., the formation of volcanoes, evolution of magma chambers and the formation of multiple lava flow types, as well as the evolution and entrapment of volatile chemicals) and impact cratering (impact rock modification, cratering mechanics, and the chronologic record). FINESSE conducts multiple terrestrial field campaigns (Craters of the Moon National Monument and Preserve in Idaho for volcanics, and West Clearwater Impact Structure in Canada for impact studies) to study such features as analogs relevant to our moon, Phobos, Deimos, and asteroids. Here we present the science and exploration results from two deployments to Idaho (2014, 2015) and our first deployment to Canada (2014). FINESSE was selected as a research team by NASA's Solar System Exploration Research Virtual Institute (SSERVI). SSERVI is a joint effort by NASA's Science Mission Directorate (SMD) and Human Exploration and Operations Mission Directorate (HEOMD).

FINESSE↗

Application of Solar Electric Propulsion to the Low Thrust Lunar Transit of the Gateway Power and Propulsion Element

NASA has committed to returning to the moon, landing the first woman and the next man on its surface. To support a sustained lunar presence, NASA will assemble an orbital platform in a quasi-stable orbit near the moon known as a Near Rectilinear Halo Orbit (NRHO). This platform, known as Gateway, will support long duration exploration missions targeting the lunar south pole. An architecture simplification implemented in 2020 combined the first two elements of the Gateway together onto a single commercial launch vehicle (CLV). When launched, the Power and Propulsion Element (PPE) and the Habitation and Logistics Outpost (HALO) will form the initial capability of NASA’s Gateway. The PPE, with its high-power Solar Electric Propulsion (SEP) system, will propel the combined vehicle from an elliptical Earth parking orbit to the target NRHO. A transit of such a large mass, delivered to the moon from a single launch vehicle, is only made possible using the highly efficient SEP system. Delivering the same mass via more traditional chemical propulsion systems would require major modifications to the mission architecture, significantly more propellant mass, and could necessitate the use of a more powerful launch vehicle. This paper describes the design of the nominal low-thrust transit by which Gateway will be delivered to the NRHO utilizing the PPE SEP system. Additionally, this paper captures how the unique capabilities of the PPE electric propulsion system have guided the design of the trajectory and how mission requirements have, in turn, impacted the maturation of the SEP system.

electric propulsion↗

Atmospheric Chemistry Over Southern Africa

During the southern African dry season, regional haze from mixed industrial pollution, biomass burning aerosol and gases from domestic and grassland fires, and biogenic sources from plants and soils is worsened by a semi-permanent atmosphere gyre over the subcontinent. These factors were a driver of several major international field campaigns in the 1990s and early 2000s, and attracted many scientists to the region. Some researchers were interested in understanding fundamental processes governing chemistry of the atmosphere and interaction with climate change. Others found favorable conditions for evaluating satellite-derived measurements of atmospheric properties and a changing land surface. With that background in mind a workshop on atmospheric chemistry was held in South Africa. Sponsored by the International Commission for Atmospheric Chemistry and Global Pollution (ICACGP; http://www.icacgp.org/), the workshop received generous support from the South African power utility, Eskom, and the Climatology Research Group of the University of the Witwatersrand, Johannesburg, South Africa. The purpose of the workshop was to review some earlier findings as well as more recent findings on southern African climate vulnerability, chemical changes due to urbanization, land-use modification, and how these factors interact. Originally proposed by John Burrows, president of ICACGP, the workshop was the first ICACGP regional workshop to study the interaction of air pollution with global chemical and climate change. Organized locally by the University of the Witwatersrand, the workshop attracted more than 60 delegates from South Africa, Mozambique, Botswana, Zimbabwe, France, Germany, Canada, and the United States. More than 30 presentations were given, exploring both retrospective and prospective aspects of the science. In several talks, attention was focused on southern African chemistry, atmospheric pollution monitoring, and climate processes as they were studied in the field campaigns such as Transport and Atmospheric Chemistry Near the Equator-Atlantic (TRACE-A), Southern African Fire-Atmosphere Research Initiative (SAFARI-92), and Southern African Regional Science Initiative (SAFARI 2000). Since those large international efforts, satellites have matured enough to enable quantifiable measurements of regional land surface, atmosphere, and ocean. In addition, global and chemical transport models have also been advanced to incorporate various data. Thus, the timing of the workshop was right for a full-fledged re-assessment of the chemistry, physics, and socio-economical impacts caused by pollution in the region, including a characterization of sources, deposition, and feedbacks with climate change.

Gatebe, Charles K.↗

Radiative Effect of Clouds on Tropospheric Chemistry in a Global Three-Dimensional Chemical Transport Model

Clouds exert an important influence on tropospheric photochemistry through modification of solar radiation that determines photolysis frequencies (J-values). We assess the radiative effect of clouds on photolysis frequencies and key oxidants in the troposphere with a global three-dimensional (3-D) chemical transport model (GEOS-CHEM) driven by assimilated meteorological observations from the Goddard Earth Observing System data assimilation system (GEOS DAS) at the NASA Global Modeling and Assimilation Office (GMAO). We focus on the year of 2001 with the GEOS-3 meteorological observations. Photolysis frequencies are calculated using the Fast-J radiative transfer algorithm. The GEOS-3 global cloud optical depth and cloud fraction are evaluated and generally consistent with the satellite retrieval products from the Moderate Resolution Imaging Spectroradiometer (MODIS) and the International Satellite Cloud Climatology Project (ISCCP). Results using the linear assumption, which assumes linear scaling of cloud optical depth with cloud fraction in a grid box, show global mean OH concentrations generally increase by less than 6% because of the radiative effect of clouds. The OH distribution shows much larger changes (with maximum decrease of approx.20% near the surface), reflecting the opposite effects of enhanced (weakened) photochemistry above (below) clouds. The global mean photolysis frequencies for J[O1D] and J[NO2] in the troposphere change by less than 5% because of clouds; global mean O3 concentrations in the troposphere increase by less than 5%. This study shows tropical upper tropospheric O3 to be less sensitive to the radiative effect of clouds than previously reported (approx.5% versus approx.20-30%). These results emphasize that the dominant effect of clouds is to influence the vertical redistribution of the intensity of photochemical activity while global average effects remain modest, again contrasting with previous studies. Differing vertical distributions of clouds may explain part, but not the majority, of these discrepancies between models. Using an approximate random overlap or a maximum-random overlap scheme to take account of the effect of cloud overlap in the vertical reduces the impact of clouds on photochemistry but does not significantly change our results with respect to the modest global average effect.

Liu, Hongyu↗