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At least 217 records · Page 12

Trypsin digestion for determining orientation of ATPase in Halobacterium saccharovorum membrane vesicles

Membranes prepared by low pressure disruption of cells exhibited no ATPase activity in the absence of Triton X-100, although 43% of the total menadione reductase activity was detected. Trypsin digestion reduced menadione reductase activity by 45% whereas ATPase activity was not affected. Disruption of the membrane fraction at higher pressure solubilized about 45% of the ATPase activity. The soluble activity was still enhanced by Triton X-100, suggesting that the detergent, besides disrupting membrane vesicles, also activated the ATPase. The discrepancy in localization of menadione reductase and ATPase activities raised questions regarding the reliability of using a single marker enzyme as an indicator of vesicle orientation.

NASA Center ARC↗

Biofilm Study Under Simulated Microgravity

The goal of this study was to understand biofilm formation under microgravity (µg), in support of biofilm mitigation efforts in exploration water recovery systems. The technical approach was to conduct a mass transfer and bacterial culture study under both simulated µg and ambient gravity. The aim was to correlate nutrient consumption to gene expression to better understand biofilm formation. A representative species of bacteria that is commonly cultured from the International Space Station (ISS) Water Processor Assembly (WPA) was cultured in a WPA influent water ersatz formulation that is tailored for microbiology studies. A mass transfer rate study was carried out using the ersatz WPA influent water by introducing a water-soluble dye to represent dissolved nutrients and nutrient particles. Imaging of dye diffusion over time allowed for the comparison of mass transport rates under a series of rotation per minute (RPM) speeds for the High Aspect Ratio Vessels (HARVs) on a Rotating Wall Vessel (RWV). This was done to determine the speed that will most accurately simulate the low convective rates experienced under actual µg conditions. Three biological replicates of the Burkholderia contaminans (B. contaminans) microbe were cultured under simulated µg with a rotating (R) control in the horizontal plane at the determined optimal RPM of 15, along with a stationary (S) reference culture. At T=0, and then at T=1,2,3 (in exponential phase) and T=4 (in S phase), the bacterial culture and ersatz were harvested for transcriptomic and nutrient content analysis, respectively. The experimental results illustrated that phosphate is a limiting nutrient in the WPA ersatz formula. Nutrient analysis illustrated that the µg treatment culture took up essential nutrients more rapidly than the R and S control cultures, yet non-essential nutrients remained higher in the µg treatment than in the controls at later timepoints. The rapid uptake and subsequent starvation of phosphate in the culture under µg conditions is further illustrated in the transcriptomic response when compared to that of the R control condition. The subsequent starvation response may serve as one element to explain a moderate enhancement of biofilm formation in the µg treatment. One implication of this work is that biofilm mitigation in the ISS environment could be supported by ensuring a steady flow of water as a vehicle for phosphate within the WPA to avoid complete phosphate consumption, which occurs in times of no flow and leads to undesired biofilm formation.

Aubrie O’Rourke↗

Inerting Aircraft Fuel Systems Using Exhaust Gases

Our purpose in this proposal was to determine the feasibility of using carbon dioxide, possibly obtained from aircraft exhaust gases as a substance to inert the fuel contained in fuel tanks aboard aircraft. To do this, we decided to look at the effects carbon dioxide has upon commercial Jet-A aircraft fuel. In particular, we looked at the solubility of CO2 in Jet-A fuel, the pumpability of CO2-saturated Jet-A fuel, the flashpoint of Jet-A fuel under various mixtures of air and CO2, the static outgassing of CO2-Saturated Jet-A fuel and the dynamic outgassing of Jet-A fuel during pumping of Jet-A fuel.

Hehemann, David G.↗

Perchlorate on Mars - Overview and Implications

Perchlorate was first detected on Mars by the Wet Chemistry Laboratory (WCL) instrument on the Phoenix lander at a concentration of ~0.5 wt% in northern plains soils. Since that initial detection, perchlorate (and likely chlorate) have been detected on Mars by both surface and orbital instruments. Perchlorate (ClO4-) is an oxidized chlorine compound and salts of perchlorate are kinetically stable (though very reactive at high temperature), very soluble, deliquescent, and have low eutectic temperature (which decreases the temperature for stable liquids on Mars). Chlorate (ClO3-) salts are similar, though they are less kinetically stable than perchlorates. Because many of the analytical signatures of perchlorate and chlorate are similar to the instruments we have used on Mars, we cannot always determine which species is present, so we will use the more generic term “oxychlorine” when referring to perchlorate and/or chlorate.

Archer, P. D.↗

Reforming and decomposition of glucose in an aqueous phase

Exploratory experiments have been carried out to study the decomposition of glucose, a typical carbohydrate, in a high temperature-high pressure water reactor. The objective of the study was to examine the feasibility of such a process to decompose cellulosic waste materials in long-term space missions. At temperatures below the critical point of water, glucose decomposed to form liquid products and char. Little gas was noted with or without reforming catalysts present. The rate of the primary glucose reaction increased significantly with temperature. Partial identification of the liquid phase was made and the C:H:O ratios determined for both the liquid and solid products. One of the more interesting results from this study was the finding that when glucose was injected into a reactor held at the critical temperature (and pressure) of water, no solid products formed. Gas production increased, but the majority of the carbon was found in soluble furans (and furan derivatives). This significant result is now being investigated further.

Amin, S.↗

Effect of ohmic, mass-transfer, and kinetic resistances on linear-sweep voltammetry in a cylindrical-pore electrode

A means is presented to account for the effect of ohmic, mass-transfer, and kinetic resistances on linear-sweep voltammograms by modeling a pore in a porous matrix as a cylindrical-pore electrode, and solving the mass and charge conservation equations in the context of this geometry for the simply redox reaction O + ne(-) yield R where both O and R are soluble species. Both analytical and numerical techniques are used to solve the governing equations. The calculated peak currents and potentials are correlated by empirical formulas to the measurable parameters: sweep rate, concentration of the redox species, diffusion coefficient, conductivity of the electrolyte, and pore dimensions. Using the correlations, a methodology is established for determining if the redox reaction kinetics are irreversible or reversible (Nernstian). If the reaction is irreversible, it is shown how the standard rate constant and the transfer coefficient may be extracted from linear-sweep voltammetry data, or, if the reaction is reversible, how the number of electrons transferred may be deduced.

Weidner, John W.↗

Space Environmentally Stable Polyimides and Copolyimides

Polyimides with a unique combination of properties including low color in thin films, atomic oxygen (AO), ultra-violet (UV) radiation resistance, solubility in organic solvents in the imide form, high glass transition (T(sub g)) temperatures and high thermal stability have been prepared and characterized. The polymers were prepared by reacting a novel aromatic diamine with aromatic dianhydrides in a polar aprotic solvent. The solubility of the polymers in the imide form as well as the color density of thin films were dependent upon the chemical structure of the dianhydride. Several thin films (25-50 mm thick) prepared by solution casting of amide acid or imide solutions exhibited very low color and high optical transparency (approximately 90%) as determined by UV/visible spectroscopy. The polymers exhibited T(sub g)s >200 C depending upon the structure of the dianhydride and temperatures of 5% weight loss approximately 500C in air as determined by dynamic thermogravimetric analysis. Thin films coated with silver/inconel were exposed to a high fluence of AO and 1000 equivalent solar hours of UV radiation. The effects of these exposures on optical properties were minor. These space environmentally durable polymers are potentially useful in a variety of applications on spacecraft such as thin film membranes on antennas, second-surface mirrors, thermal/optical coatings and multi-layer thermal insulation (MLI) blanket materials. The chemistry, physical and mechanical properties of the polymers as well as their responses to AO and UV exposure will be discussed.

Watson, Kent A.↗

A Preliminary Investigation of the E-Beam Induced Polymerization of Maleimide and Norbornene End-capped Polyimides

A research area of high activity in connection with aerospace engineering has been the development of polymer thermosetting resins that can resist temperature as high as 300 C while maintaining adequate toughness, and providing ease of processing to enable low temperature and low cost composite fabrication methods. In order to meet such requirements, sequential interpenetrating polymer networks (IPNs) based on bismaleimide (BMI) and cyanate ester (CE) monomers were investigated. In these systems, a polycyanurate network is first formed in the presence of BMI and appropriate reactive diluent monomers and in a second step, a network based on the BMI is created in the presence of a fully formed polycyanurate network. The materials developed can be processed at relatively low temperature (less than 150 C) and with the aid of electron beam (EB) curing. Of major importance to the success of this work was the identification of a reactive diluent that improves ease of processing and has tailored reactivity to allow for the controlled synthesis of CE-BMI sequential IPNs. Based on solubility and reactivity of a number of reactive diluents, N-acryloylmorpholine (AMP) was selected as a comonomer for BMI copolymerization. A donor-acceptoreaction mechanism was suggested to explain the relative reactivity of a variety of reactive diluents towards maleimide functionality. The optimum processing parameters for the formation of the first network were determined through the study of metal catalyzed cure and hydrolysis of cyanate esters, whereas the reaction behavior for second network formation in terms of the influence of EB dose rate and temperature was elucidated through an in-situ kinetics study of maleimide and AMP copolymerization. Structure-property relationships were developed which allowed for the design of improved resin systems. In particular, appropriate network coupler possessing cyanate ester and maleimide functionality was synthesized to link the polycyanurate first network to the BMI/AMP second network and thus form linked sequential IPNs (LIPNs). Consequently, Tg as high as 370 C was achieved and a fracture toughness of 120 Joules per square meters was obtained for resin systems that possess adequately low viscosity for processing using liquid molding techniques at low temperature.

Palmese, Giuseppe R.↗

Stability of chromium (III) sulfate in atmospheres containing oxygen and sulfur

The stability of chromium sulfate in the temperature range from 880 K to 1040 K was determined by employing a dynamic gas-solid equilibration technique. The solid chromium sulfate was equilibrated in a gas stream of controlled SO3 potential. Thermogravimetric and differential thermal analyses were used to follow the decomposition of chromium sulfate. X-ray diffraction analysis indicated that the decomposition product was crystalline Cr2O3 and that the mutual solubility between Cr2(SO4)3 and Cr2O3 was negligible. Over the temperature range investigated, the decomposition pressure were significantly high so that chromium sulfate is not expected to form on commercial alloys containing chromium when exposed to gaseous environments containing oxygen and sulfur (such as those encountered in coal gasification).

Jacob, K. T.↗

Mineralogy of the Martian Surface: Crustal Composition to Surface Processes

Over the course of this award we have: 1) Completed and published the results of a study of the effects of hyperfine particles on reflectance spectra of olivine and quartz, which included the development of scattering codes. Research has also progressed in the analysis of the effects of fine particle sizes on clay spectra. 2) Completed the analysis of the mineralogy of dark regions, showed the insitu compositions are highly correlated to the SNC meteorites, and determined that the martian mantle was depleted in aluminum prior to 2-3 GA ago; Studies of the mineralogic heterogeneity of surficial materials on Mars have also been conducted. and 3) Performed initial work on the study of the physical and chemical processes likely to form and modify duricrust. This includes assessments of erosion rates, solubility and transport of iron in soil environments, and models of pedogenic crust formation.

Mustard, John F.↗

Determination of the Fe-rich portion of the Fe-Ni-C phase diagram

The iron-enriched section of the phase diagram for the ternary alloy Fe-Ni-C of various compositions is determined at 773, 873, 923, and 1003 C. The two-phase tie lines and three-phase tie triangles are measured by electron microprobe analyses. Tie lines in samples without bulk equilibrium are obtained by extrapolated interface compositions under the assumption of local equilibrium at the interface. It is shown that Ni addition somewhat reduces carbon solubility in austenite while decreasing the stability of the carbide phase. In particular, the carbide is always poor in Ni relative to the coexisting metal phase(s).

Romig, A. D., Jr.↗

Roles of Poly(propylene Glycol) During Solvent-Based Lamination of Ceramic Green Tapes

Solvent lamination for alumina green tapes is readily accomplished using a mixture of ethanol, toluene and poly(propylene glycol). After lamination, the PPG is clearly present as a discrete film at the interface between the laminated tapes. This condition, however, does not generate delamination during firing. Systematic sets of experiments are undertaken to determine the role of PPG in the lamination process and, specifically, the mechanism by which it is redistributed during subsequent processing. PPG slowly diffuses through the organic binder film at room temperature. The PPG diffusion rapidly increases as temperature is increased to 80 C. The key to the efficiency of adhesives during green-tape lamination is mutual solubility of the nonvolatile component of the glue and the base polymeric binder.

Suppakarn, Nitinat↗

Solubility and Cation Exchange Properties of Synthetic Hydroxyapatite and Clinoptilolite Mixtures

A zeoponic plant growth system is defined as the cultivation of plants in artificial soils, which have zeolites as a major component. These systems: 1) can serve as a controllable and renewable fertilization system to provide plant growth nutrients; 2) can mitigate the adverse effects of contamination due to leaching of highly soluble and concentrated fertilizers; and 3) are being considered as substrates for plant growth in regenerative life-support systems for long-duration space missions. Batch-equilibrium studies of the dissolution and ion-exchange properties of mixtures of naturally-occurring Wyoming clinoptilolite (a zeolite) exchanged with K(+) or NH4(+); and synthetic hydroxyapatite were conducted to determine: 1) the plant availability of the macro-nutrients NH4-N, P, K, Ca, and Mg and 2) the effects of varying the clinoptilolite to hydroxyapatite ratio and the ratio of exchangeable cations (K(+) vs. NH4(+)) on clinoptilolite extraframework sites. The nutrients NH4-N (19.7 to 73.6 mg L(sup -1), P (0.57 to 14.99 mg L(sup- 1), K (14.8 to 104.9 mg L(sup -1), and Mg (0.11 to 6.68mg L(sup -1) are available to plants at sufficient levels. Solution Ca concentrations (0.47 to 3.40 mg L(sup -1) are less than optimal. Solution concentrations of NH4(+), K(+), Ca(2+), and Mg(2+) all decreased with increasing clinoptilolite to hydroxyapatite ratio in the sample. Solution concentrations of phosphorous initially increased, reached a maximum value and then decreased with increasing clinoptilolite to hydroxyapatite ratio in the sample. The NH4(+) -exchanged clinoptilolite is more efficient in dissolving synthetic hydroxyapatite than the K(+) -exchanged clinoptilolite. This suggests that NH4(+), which is less selective at clinoptilolite extraframework sites than K(+) is exchanged more readily by Ca(2+) and thereby enhances the dissolution of the synthetic hydroxyapatite.

Beiersdorfer, Raymond E.↗

Development of Low Density Titanium Alloys for Structural Applications

In this report the results of a program designed to reduce the density of titanium by adding magnesium are presented. Because these two elements are immiscible under conventional ingot metallurgy techniques, two specialized powder metallurgy methods namely, mechanical alloying (MA) and physical vapor deposition (PVD) were implemented. The mechanical alloying experiments were done both at the University of Idaho and at the Defense Research Agency in UK. Since titanium is reactive with interstitial elements, a secondary goal of this research was to correlate solubility extensions with interstitial contamination content, especially oxygen and nitrogen. MA was carried out in SPEX 8000 shaker mils and different milling containers were utilized to control the level of contamination. Results showed that solubilities of Mg in Ti were obtained up to 28 at.% (16.4 wt. %) Mg in Ti for Ti-39.6 at. % (25 wt. %) Mg alloys, which greatly exceed those obtained under equilibrium conditions. This reflects a density reduction of approximately 26 %. Contamination of oxygen and nitrogen seemed to increase the solubility of magnesium in titanium in some cases; however, we were not able to make a clear correlation between contamination levels with solubilities. Work at the DRA has emphasized optimization of present PVD equipment, specifically composition and temperature control. Preliminary PVD data has shown Ti-Mg deposits have successfully been made up to 2 mm thick and that solubility extensions were achieved. The potential for density reduction of titanium by alloying with magnesium has been demonstrated; however, this work has only scratched the surface of the development of such low density alloys. Much research is needed before such alloys could be implemented into industry. Further funding is required in order to optimize the MA/PVD processes including contamination control, determination of optimal alloy compositions, microstructure development, and mechanical property determination.

Froes, F. H.↗

Thermal and Evolved Gas Behavior of Calcite Under Mars Phoenix TEGA Operating Conditions

The Mars Phoenix Scout Mission with its diverse instrument suite successfully examined several soils on the Northern plains of Mars. The Thermal and Evolved Gas Analyzer (TEGA) was employed to detect organic and inorganic materials by coupling a differential scanning calorimeter (DSC) with a magnetic-sector mass spectrometer (MS). Martian soil was heated up to 1000 C in the DSC ovens and evolved gases from mineral decomposition products were examined with the MS. TEGA s DSC has the capability to detect endothermic and exothermic reactions during heating that are characteristic of minerals present in the Martian soil. Initial TEGA results indicated the presence of endothermic peaks with onset temperatures that ranged from 675 C to 750 C with corresponding CO2 release. This result suggests the presence of calcite (CaCO3. CaO + CO2). Organic combustion to CO2 is not likely since this mostly occurs at temperatures below 550 C. Fe-carbonate and Mg-carbonate are not likely because their decomposition temperatures are less than 600 C. TEGA enthalpy determinations suggest that calcite, may occur in the Martian soil in concentrations of approx.1 to 5 wt. %. The detection of calcite could be questioned based on previous results that suggest Mars soils are mostly acidic. However, the Phoenix landing site soil pH was measured at pH 8.3 0.5, which is typical of terrestrial soils where pH is controlled by calcite solubility. The range of onset temperatures and calcite concentration as calculated by TEGA is poorly con-strained in part because of limited thermal data of cal-cite at reduced pressures. TEGA operates at <30 mbar while most calcite literature thermal data was obtained at 1000 mbar or higher pressures.

Ming, D.W.↗

Tensile Properties of Hydrogels and of Snake Skin

Stimulus-responsive or 'smart' gels are of potential interest as sensors and actuators, in industrial separations, and as permeable delivery systems. In most applications, a certain degree of mechanical strength and toughness will be required, yet the large-strain behavior of gels has not been widely reported. Some exceptions include work on gelatin and other food gels, some characterization of soft gels applicable for in-vitro cell growth studies, and toughness determinations on commercial contact lens materials. In general, it can be anticipated that the gel stiffness will increase with increasing degree of crosslinking, but the tensile strength may go through a maximum. Gel properties can be tailored by varying not only the degree of crosslinking, but also the polymer concentration and the nature of the polymer backbone (e.g. its stiffness or solubility). Polypeptides provide an especially interesting case, where secondary structure affects trends in moduli and conformational transitions may accompany phase changes. A few papers on the tensile properties of responsive gels have begun to appear. The responsive hydrogel chosen for the present study, crosslinked hydroxypropylcellulose, shrinks over a rather narrow temperature range near 44 C. Some vertebrate skin is also subject to substantial strain. Among reptiles, the morphologies of the skin and scales show wide variations. Bauer et al. described the mechanical properties and histology of gecko skin; longitudinal tensile properties of snake skin were examined by Jayne with reference to locomotion. The present measurements focus on adaptations related to feeding, including the response of the skin to circumferential tension. Tensile properties will be related to interspecific and regional variation in skin structure and folding.

Hinkley, Jeffrey A.↗

Enantiomeric and Isotopic Analysis of Organic Compounds in Carbonaceous Meteorites

Carbonaceous meteorites are relatively enriched in soluble organic compounds. The Murchison and Murray meteorites contain numerous compounds of interest in the study of early solar system organic chemistry and organic compounds of potential importance for the origin of life. These include: amino acids, amides, carboxylic acids, and polyols. This talk will focus on the enantiomeric and isotopic analysis of individual meteoritic compounds - primarily polyol acids. The analyses will determine if, in addition to certain amino acids from Murchison, another potentially important class of prebiotic compounds also contains enantiomeric excesses, i.e., excesses that could have contributed to the current homochirality of life. Preliminary enantiomeric and isotopic (C- 13) measurements of Murchison glyceric acid show that it is indeed extraterrestrial. C-13 and D isotope analysis of meteoritic sugar alcohols (glycerol, threitol, ribitol, etc.) has shown that they are also indigenous to the meteorite.

Cooper, George↗

The MSP 2001 Mars Environmental Compatibility Assessment (MECA)

The Mars Environmental Compatibility Assessment (MECA) will evaluate the Martian environment for soil and dust-related hazards to human exploration as part of the Mars Surveyor Program 2001 Lander. Sponsored by the Human Exploration and Development of Space (HEDS) enterprise, MECA's goal is to evaluate potential geochemical and environmental hazards that may confront future Martian explorers, and to guide HEDS scientists in the development of high fidelity Mars soil simulants. The integrated MECA payload contains a wet-chemistry laboratory, a microscopy station, an electrometer to characterize the electrostatics of the soil and its environment, and arrays of material patches to study the abrasive and adhesive properties of soil grains. The instrument will acquire soil samples with a robotic arm equipped with a camera. MECA will examine surface and subsurface soil and dust in order to characterize particle size, shape, hardness, and also physical characteristics that may provide clues to mineralogy. MECA will characterize soil/water mixtures with respect to pH, redox potential, total dissolved ions, and trace toxins. MECA will determine the nature of electrostatic charging associated with excavation of soil, and the influence of ionizing radiation on material properties. It will also observe natural dust accumulation on engineering materials. To accomplish these objectives, MECA is allocated a mass of 10 kg within an enclosure of 35 x 25 x 15 cm. The Wet Chemistry Laboratory (WCL) consists of four identical cells that will accept samples from surface and subsurface regions accessible to the Lander's robotic arm, mix them with water, and perform extensive analysis of the solution. Ion-selective electrodes and related sensors will evaluate total dissolved solids, redox potential, pH, and the concentration of many soluble ions and gases in wet Martian soil. These electrodes can detect potentially dangerous heavy-metal ions, emitted pathogenic gases, and the soil's corrosive potential. Experiments will include cyclic voltammetry and anodic stripping voltammetry. Complementary to the Viking experiments, the chemical laboratory will characterize the water-soil solution rather than emitted gases. Nonetheless, through analysis of dissolved gases it will be able to replicate many of the Viking observations related to oxidants. MECA's microscopy station combines optical and atomic-force microscopy (AFM) in an actively focused, controlled illumination environment to image particles from millimeters to nanometers in size. Careful selection of substrates allows controlled experiments in adhesion, abrasion, hardness, aggregation, magnetic and other properties. Special tools allow primitive manipulation (brushing and scraping) of samples. Soil particle properties including size, shape, color, hardness, adhesive potential (electrostatic and magnetic), will be determined using an array of sample receptacles and collection substrates. The simple, rugged atomic-force microscope will image in the submicron size range and has the capability of performing a particle-by-particle analysis of the dust and soil. On Earth, the earliest forms of life are preserved as microfossils. The atomic-force microscope will have the required resolution to image down to the scale of terrestrial microfossils and beyond. Mounted on the end of the robot arm, MECA's electrometer actually consists of four types of sensors: an electric field meter, several triboelectricity monitors, an ion gauge, and a thermometer. Tempered only by ultraviolet-light-induced ions and a low-voltage breakdown threshold, the dry, cold, dusty martian environment presents an imposing electrostatic hazard to both robots and humans. The field meter will measure the ambient field on nearby objects while the triboelectric sensors, using identical circuitry, will measure the charge accumulated on test substances as they are dragged through the soil by the arm. The ion chamber, open to the environment, will sense both charged dust and free ions in the air. Over and above the potential threat to electronics, the electrostatic environment holds one of the keys to transport of dust and, consequently, Martian meteorology. Viewed with the robot arm camera, the abrasion and adhesion plates are strategically placed to allow direct observation of the interaction between materials and soils on a macroscopic scale. Materials of graded hardness are placed directly under the robot arm scoop to sense wear and soil hardness. A second array, placed on the lander deck, is deployed after the dust plume of landing has settled. It can be manipulated in a primitive fashion by the arm, first having dirt deposited on it from the scoop and subsequently shaken clean. A third array will passively collect dust from the atmosphere. In addition to objectives related to human exploration, the MECA data set will be rich in information relevant to basic geology, paleoclimate, and exobiology issues. To understand both contemporaneous and ancient processes on Mars, the mineralogy, petrology, and reactivity of Martian surface materials should be constrained. The MECA experiment will shed light on these quantities through its combination of chemistry and microscopy. MECA will be capable of measuring the composition of ancient surface water environments, observing microscopic evidence of geological (and biological?) processes, inferring soil and dust transport, comminution and weathering mechanisms, and characterizing soil horizons that might be encountered during excavation.

Hecht, M. H.↗