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At least 379 records · Page 21

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NASA NTRS1995

Crystalline imide/arylene ether copolymers

Crystalline imide/arylene ether block copolymers are prepared by reacting anhydride terminated poly(amic acids) with amine terminated poly)arylene ethers) in polar aprotic solvents and chemically or thermally cyclodehydrating the resulting intermediate poly(amic acids). The block copolymers of the invention have one glass transition temperature or two, depending on the particular structure and/or the compatibility of the block units. Most of these crystalline block copolymers for tough, solvent resistant films with high tensile properties. While all of the copolymers produced by the present invention are crystalline, testing reveals that copolymers with longer imide blocks or higher imide content have increased crystallinity.

Jensen, Brian J.↗

NASA NTRS1995

Synthesis of low color, atomic oxygen resistant polyimides

The purpose of this project was to develop low color, atomic oxygen resistant polyimides for potential applications on spacecraft in low earth orbit. The material is needed in order to protect satellites and spacecraft from the gases and radiation found at those altitudes. Phosphorous containing polyimides have been shown to be especially resistant to corrosion and weight loss under oxygen plasma. Unfortunately the color of these phosphorous containing polyimides is still too high for them to be good heat insulators. While they are not as effective as teflon, the current material of choice. polyimides are much less dense than teflon and would be especially valuable if they could be made with low color. The approach taken was to synthesize a monomer which would contain the elements needed for giving the final polyimide its desired properties. In particular the monomer should incorporate phosphine or phosphine oxides and have bulky side groups to block any color forming charge transfer structures. The target molecule, 3,5-di-(trifluoromethylphenyl)-bis(3-aminophenyl) phosphine oxide, (containing both a phosphine oxide group and a bulky ditrifluoromethylphenyl group) was synthesized via three reactions in overall yield of 21 percent. In addition, a model compound, bis(3-phenylamine) phenyl phosphine oxide, was synthesized two different ways in order to establish the conditions for the nitration of phosphine oxides and their reduction to the amine. Finally, a trisubstituted phosphine oxide was synthesized. In all, seven phosphorus containing organic compounds were synthesized, purified and characterized. The model compound was reacted with oxydiphthalic anhydride to form a polyamic acid with inherent viscosity of 0.34. This material was cast into a film and heated, forming a normally colored fairly strong polyimide with a Tg of 240 C. The target compound was reacted with 6-fluorodiphthalic anhydride to give a polyamic acid with inherent viscosity of 0.19 and cast to give a heavily cracked colored film with a Tg of 230 C.

MacInnes, Dave↗

NASA NTRS1996

Dextroamphetamine: a pharmacologic countermeasure for space motion sickness and orthostatic dysfunction

Dextroamphetamine has potential as a pharmacologic agent for the alleviation of two common health effects associated with microgravity. As an adjuvant to Space Motion Sickness (SMS) medication, dextroamphetamine can enhance treatment efficacy by reducing undesirable Central Nervous System (CNS) side effects of SMS medications. Secondly, dextroamphetamine may be useful for the prevention of symptoms of post-mission orthostatic intolerance caused by cardiovascular deconditioning during spaceflight. There is interest in developing an intranasal delivery form of dextroamphetanmine for use as a countermeasure in microgravity conditions. Development of this dosage form will require an analytical detection method with sensitivity in the low ng range (1 to 100 ng/mL). During the 1995 Summer Faculty Fellowship Program, two analytical methods were developed and evaluated for their suitability as quantitative procedures for dextroamphetamine in studies of product stability, bioavailability assessment, and pharmacokinetic evaluation. In developing some of the analytical methods, beta-phenylethylamine, a primary amine structurally similar to dextroamphetamine, was used. The first analytical procedure to be evaluated involved hexane extraction and subsequent fluorescamine labeling of beta-phenylethylamine. The second analytical procedure to be evaluated involved quantitation of dextroamphetamine by an Enzyme-Linked ImmunoSorbent Assay (ELISA).

Snow, L. Dale↗

NASA NTRS1995

An IRAS-Based Search for New Dusty Late-Type WC Wolf-Rayet Stars

I have examined all Infrared Astronomical Satellite (IRAS) data relevant to the 173 Galactic Wolf-Rayet (W-R) stars in an updated catalog, including the 13 stars newly discovered by Shara and coworkers. Using the W-R coordinates in these lists, I have examined the IRAS Point Source Catalog (PSC), the Faint Source Catalog, and the Faint Source Reject Catalog, and have generated one-dimensional spatial profiles, 'ADDSCANs', and two-dimensional full-resolution images, 'FRESCOS'. The goal was to assemble the best set of observed IRAS color indices for different W-R types, in particular for known dusty late-type WC Wolf-Rayet (WCL) objects. I have also unsuccessfully sought differences in IRAS colors and absolute magnitudes between single and binary W-R stars. The color indices for the entire ensemble of W-R stars define zones in the IRAS color-color ([12] - [25], [25] - [60])-plane. By searching the PSC for otherwise unassociated sources that satisfy these colors, I have identified potential new W-R candidates, perhaps too faint to have been recognized in previous optical searches. I have extracted these candidates' IRAS low-resolution spectrometer (LRS) data and compared the spectra with the highly characteristic LRS shape for known dusty WCL stars. The 13 surviving candidates must now be ex amined by optical spectroscopy. This work represents a much more rigorous and exhaustive version of the LRS study that identified IRAS 17380 - 3031 (WR98a) as the first new W-R (WC9) star discovered by IPAS. This search should have detected dusty WCL stars to a distance of 7.0 kpc from the Sun, for l is greater than 30 degrees, and to 2.9 kpc even in the innermost galaxy. For free-free-dominated W-R stars the corresponding distances are 2.5 and 1.0 kpc, respectively.

Cohen, Martin↗

NASA NTRS1997

Structure-Property Relationships of Bismaleimides

The purpose of this research was to control and systematically vary the network topology of bismaleimides through cure temperature and chemistry (addition of various coreactants) and subsequently attempt to determine structure-mechanical property relationships. Characterization of the bismaleimide structures by dielectric, rheological, and thermal analyses, and density measurements was subsequently correlated with mechanical properties such as modulus, yield strength, fracture energy, and stress relaxation. The model material used in this investigation was 4,4'-BismaleiMidodIphenyl methane (BMI). BMI was coreacted with either 4,4'-Methylene Dianiline (MDA), o,o'-diallyl bisphenol A (DABA) from Ciba Geigy, or Diamino Diphenyl Sulfone (DDS). Three cure paths were employed: a low- temperature cure of 140 C where chain extension should predominate, a high-temperature cure of 220 C where both chain extension and crosslinking should occur simultaneously, and a low-temperature (140 C) cure followed immediately by a high-temperature (220 C) cure where the chain extension reaction or amine addition precedes BMI homopolymerization or crosslinking. Samples of cured and postcured PMR-15 were also tested to determine the effects of postcuring on the mechanical properties. The low-temperature cure condition of BMI/MDA exhibited the highest modulus values for a given mole fraction of BMI with the modulus decreasing with decreasing concentration of BMI. The higher elastic modulus is the result of steric hindrance by unreacted BMI molecules in the glassy state. The moduli values for the high- and low/high-temperature cure conditions of BMI/MDA decreased as the amount of diamine increased. All the moduli values mimic the yield strength and density trends. For the high-temperature cure condition, the room- temperature modulus remained constant with decreasing mole fraction of BMT for the BMI/DABA and BMI/DDS systems. Postcuring PMR-15 increases the modulus over that of the cured material even though density values of cured and postcured PMR were essentially the same. Preliminary results of a continuous and intermittent stress relaxation experiment for BMI:MDA in a 2:1 molar ratio indicate that crosslinking is occurring when the sample is in the undeformed state. Computer simulation of properties such as density, glass transition temperature, and modulus for the low- temperature cure conditions of BMI/MDA and BMI/DABA were completed. The computer modeling was used to help further understand and confirm the structure characterization results. The simulations correctly predicted the trends of these properties versus mole fraction BMI and were extended to other BMI/diamine systems.

Tenteris-Noebe, Anita D.↗

NASA NTRS1997

Observations and Modeling of the Transient General Circulation of the North Pacific Basin

The objective of this study was to clarify the role that interstellar-cloud chemistry played in forming the population of organic molecules presently found in carbonaceous meteorites. This goal was to be achieved by means of defining the isotopic components present in organic and related phases in the meteorites and thereby identify the processes and source reservoirs involved in organic synthesis in the early solar system. Isotopic analysis of separated amino acids from the Murchison meteorite yielded results that are complex and not fully interpretable at this time. Substantial inter-acid variability in D/H ratio was observed, some but not all of which could be attributed to exchange with terrestrial hydrogen. Pronounced, though smaller, variability was also found for N-15/N-14 ratios. For both D/H and N-15/N-14 data, observed meteoritic values were substantially greater than found in terrestrial materials, providing a robust constraint on degrees of possible terrestrial contamination. Also, C-13/C-12 ratios, though falling within the range of data found on earth, significantly exceeded those characteristic of naturally occurring terrestrial amino acids. Inter-acid variability in C-13/C-12 ratios was muted relative to that observed for D/H and N-15/N-14 but still lay well outside of experimental uncertainty. No systematic relationship could be observed between variations in H, C and N isotopes. Two anomalous components were also found during the course of this study. A highly (greater than 6% relative to terrestrial) N-15-depleted, N-rich compound, which has not yet been identified, co-eluted with some amino acids. Clearly the Murchison meteorite sampled nitrogen from a number of highly diverse isotopic reservoirs. In fact, from this and related studies, it is now apparent that the distribution of nitrogen isotopes in the primitive solar system was extremely inhomogeneous. The second anomalous result obtained in the present study was for an extract of 'ammonia' from Murchison. It should be noted that this sample consisted of ammonia that was probably derived from a number of different compounds present in the meteorite itself, possibly including amines and amides, as well as ammonia sensu strictu and ammonium slats. However, the significance of this analysis is that the N-15/N-14 ratio measured was much lower than those found for the meteoritic amino acids (+2% vs around + 9% relative to terrestrial). This raises an important question concerning the source of the ammonia that was involved in synthesis of the amino acids. This issue needs to be explored further.

Kerridge, John F.↗

NASA NTRS1995

Degradation of Coflon in Methanol at Temperatures Around 140 C

An unexpected and significant physico-chemical degradation of Coflon PVDF specimens was observed at the end of 1994 during routine scheduled exposure exercises on strained material. The intent was to age various samples, including some strained in a 4-point bend configuration, in methanol at 140 C and subsequently submit the aged samples to various tests including dynamic fatigue and fracture toughness. However, the samples deteriorated to such an extent that such testing was not possible: only when conditions were made less severe was it found possible to perform such testing. The purpose of the current report is to describe the nature of the PVDF deterioration observed during a number of tests performed to examine this phenomenon. This report also records, as Appendix 1, some SEM/X-ray microanalysis data on Coflon samples exposed to a methanol/amine mixture, and to other amine or H2S-aged samples.

Campion, R. P.↗

NASA NTRS1995

Investigation of the Prebiotic Synthesis of Amino Acids and RNA Bases from CO2 Using FeS/H2S As a Reducing Agent

An autotrophic theory of the origin of metabolism and life has been proposed in which carbon dioxide is reduced by ferrous sulfide and hydrogen sulfide by means of a reversed citric acid cycle, leading to the production of amino acids. Similar processes have been proposed for purine synthesis. Ferrous sulfide is a strong reducing agent in the presence of hydrogen sulfide and can produce hydrogen as well as reduce alkenes, alkynes, and thiols to saturated hydrocarbons and reduce ketones to thiols. However, the reduction of carbon dioxide has not been demonstrated. We show here that no amino acids, purities, or pyrimidines are produced from carbon dioxide with the ferrous sulfide and hydrogen sulfide system. Furthermore, this system does not produce amino acids from carboxylic acids by reductive amination and carboxylation. Thus, the proposed autotrophic theory, using carbon dioxide, ferrous sulfide, and hydrogen sulfide, lacks the robustness needed to be a geological process and is, therefore, unlikely to have played a role In the origin of metabolism or the origin of life.

Keefe, Anthony D.↗

NASA NTRS1998

Neural Control Mechanisms and Body Fluid Homeostasis

The goal of the proposed research was to study the nature of afferent signals to the brain that reflect the status of body fluid balance and to investigate the central neural mechanisms that process this information for the activation of response systems which restore body fluid homeostasis. That is, in the face of loss of fluids from intracellular or extracellular fluid compartments, animals seek and ingest water and ionic solutions (particularly Na(+) solutions) to restore the intracellular and extracellular spaces. Over recent years, our laboratory has generated a substantial body of information indicating that: (1) a fall in systemic arterial pressure facilitates the ingestion of rehydrating solutions and (2) that the actions of brain amine systems (e.g., norepinephrine; serotonin) are critical for precise correction of fluid losses. Because both acute and chronic dehydration are associated with physiological stresses, such as exercise and sustained exposure to microgravity, the present research will aid in achieving a better understanding of how vital information is handled by the nervous system for maintenance of the body's fluid matrix which is critical for health and well-being.

Johnson, Alan Kim↗

NASA NTRS1995

Investigation of the Prebiotic Synthesis of Amino Acids and RNA Bases from CO2 using FeS/H2S as a Reducing Agent

An autotrophic theory of the origin of metabolism and life has been proposed in which carbon dioxide is reduced by ferrous sulfide and hydrogen sulfide by means of a reversed citric acid cycle, leading to the production of amino acids. Similar processes have been proposed for purine synthesis. Ferrous sulfide is a strong reducing agent in the presence of hydrogen sulfide and can produce hydrogen as well as reduce alkenes, alkynes, and thiols to saturated hydrocarbons and reduce ketones to thiols. However, the reduction of carbon dioxide has not been demonstrated. We show here that no amino acids, purines, or pyrimidines are produced from carbon dioxide with the ferrous sulfide and hydrogen sulfide system. Furthermore, this system does not produce amino acids from carboxylic acids by reductive amination and carboxylation. Thus, the proposed autotrophic theory, using carbon dioxide, ferrous sulfide, and hydrogen sulfide, lacks the robustness needed to be a geological process and is, therefore, unlikely to have played a role in the origin of metabolism or the origin of life.

Keefe, Anthony D.↗

NASA NTRS1998

NASA Advanced Fuels Program

NASA with the USAF Research Laboratory and it's industry partners, has been conducting planning and research into advanced fuels. This work is sponsored under the NASA Advanced Space Transportation Program (ASTP). The current research focus is on Alternative Hydrocarbon fuels, Monopropellants, and Solid Cryogens for storing atoms of Hydrogen, Boron, Carbon, and Aluminum. Alternative hydrocarbons that are under consideration are bi cyclo propylidene, spiro pentane, and tri propargyl amine. These three fuels have been identified as initial candidates to increase the specific impulse of hydrocarbon fueled rockets by 10-15 seconds over 02/RP-1. Formulation of these propellants is proceeding this year, and rocket engine testing is planned for the near future. Monopropellant investigations are focused on dinitramine based fuels, and potential collaborations with the US Navy. The dinitramine fuel work is being conducted under an Small Business Innovation research (SBIR) contract with the team of Orbital Technologies Corp. (Madison, WI) and SRI (Menlo Park, CA). This work may lead to a high density, high specific impulse monopropellants that can simplify the operations for launch vehicles and spacecraft. Solid Cryogens are being considered to store atoms of Hydrogen, Boron, Carbon, and Aluminum. Stored atom propellants are potentially the highest specific impulse chemical rockets that may be practical. These fuels are composed of atoms, stored in solid cryogenic particles, suspended in a cryogenic liquid or gel. The fuel would be fed to a rocket engine as a slurry or gelled cryogenic liquid with the suspended particles with the trapped atoms. Testing is planned to demonstrate the formation of the particles, and then characterize the slurry flows. Rocket propellant and propulsion technology improvements can be used to reduce the development time and operational costs of new space vehicle programs. Advanced propellant technologies can make the space vehicles safer, more operable, and better performing. Five technology areas are described: Monopropellants, Alternative Hydrocarbons, Gelled Hydrogen, Metallized Gelled Propellants, and High Energy Density Materials. The benefits of these propellants for future vehicles are outlined using mission study results and the technologies are briefly discussed.

Palaszewski, Bryan↗

NASA NTRS1998

Fluorescence Studies of Lysozyme Nucleation

Fluorescence is one of the most powerful tools available for the study of macromolecules. For example, fluorescence can be used to study self association through methods such as anisotropy (the rotational rate of the molecule in solution), quenching (the accessibility of a bound probe to the bulk solution), and resonance energy transfer (measurement of the distance between two species). Fluorescence can also be used to study the local environment of the probe molecules, and the changes in that environment which accompany crystal nucleation and growth. However fluorescent techniques have been very much underutilized in macromolecular growth studies. One major advantage is that the fluorescent species generally must be at low concentration, typically ca 10-5 to 10-6 M. Thus one can study a very wide range of solution conditions, ranging from very high to very low protein concentration, he latter of which are not readily accessible to scattering techniques. We have prepared a number of fluorescent derivatives of chicken egg white lysozyme (CEWL). Fluorescent probes have been attached to two different sites, ASP 101 and the N-terrninal amine, with a sought for use in different lines of study. Preliminary resonance energy transfer studies have been -carried out using pyrene acetic acid (Ex 340 mn, Em 376 nm) lysozyme as a donor and cascade blue (Ex 377 run, Em 423 nm) labeled lysozyme as an acceptor. The emission of both the pyrene and cascade blue probes was followed as a function of the salt protein concentrations. The data show an increase in cascade blue and a concomitant decrease in the pyrene fluorescence as either the salt or protein concentrations are increased, suggesting that the two species are approaching each other close enough for resonance energy transfer to occur. This data can be analyzed to measure the distance between the probe molecules and, knowing their locations on the protein molecule their distances from and orientations with respect to each other. The results of these and other studies will be discussed.

Pusey, Marc L.↗

NASA NTRS1999

Fluorescence Studies of Protein Crystal Nucleation

Fluorescence can be used to study protein crystal nucleation through methods such as anisotropy, quenching, and resonance energy transfer (FRET), to follow pH and ionic strength changes, and follow events occurring at the growth interface. We have postulated, based upon a range of experimental evidence that the growth unit of tetragonal hen egg white lysozyme is an octamer. Several fluorescent derivatives of chicken egg white lysozyme have been prepared. The fluorescent probes lucifer yellow (LY), cascade blue, and 5-((2-aminoethyl)aminonapthalene-1-sulfonic acid (EDANS), have been covalently attached to ASP 101. All crystallize in the characteristic tetragonal form, indicating that the bound probes are likely laying within the active site cleft. Crystals of the LY and EDANS derivatives have been found to diffract to at least 1.7 A. A second group of derivatives is to the N-terminal amine group, and these do not crystallize as this site is part of the contact region between the adjacent 43 helix chains. However derivatives at these sites would not interfere with formation of the 43 helices in solution. Preliminary FRET studies have been carried out using N-terminal bound pyrene acetic acid (Ex 340 nm, Em 376 nm) lysozyme as a donor and LY (Ex -425 nm, Em 525 nm) labeled lysozyme as an acceptor. FRET data have been obtained at pH 4.6, 0.1 M NaAc buffer, at 5 and 7% NaCl, 4 C. The corresponding Csat values are 0.471 and 0.362 mg/ml (approximately 3.3 and approximately 2.5 x 10(exp -5) M respectively). The data at both salt concentrations show a consistent trend of decreasing fluorescence intensity of the donor species (PAA) with increasing total protein concentration. This decrease is more pronounced at 7% NaCl, consistent with the expected increased intermolecular interactions at higher salt concentrations reflected in the lower solubility. The calculated average distance between any two protein molecules at 5 x 10(exp -6) M is approximately 70nm, well beyond the range where any FRET can be expected. Results from these and ongoing studies will be presented.

Pusey, Marc L.↗

NASA NTRS1971

Phenol Analysis -- Some Analytical Considerations

Contamination of potable water supplies with halogenated phenols in concentrations of 2-10 parts per billion (ppb) produces objectionable tastes and odors capable of influencing consumer acceptability. Routine analysis by the distillation/ 4-aminoantipyrine method is limited by lack of sensitivity and subject to interference by aryl amines. This has been overcome by developing a continuous liquid-liquid extraction system to selectively isolate phenols and eliminate major interfering substances. Stable reagents have been formulated to reduce blank color and extend sensitivity. Equipment suitable for analysis of phenols at the 1 ppb level or less in 20 minutes is described.

Starkey, R. J., Jr.↗

NASA NTRS2000

Aging Effects of Environmentally-Friendly Cleaners on Adhesive Bond Integrity

Because of the 1990 Clean Air Act Amendment many chlorinated solvents are being phased out of use in manufacturing industries. Replacement of the ODC (ozone- depleting chemicals) with less volatile, non-ozone depleting cleaners has been extensively studied over the past nine years at Thiokol Propulsion, Cordant Technologies. Many of the non-ODC cleaners contain compounds that can potentially degrade over time under conditions of high temperature, humidity and exposure to light. The chemical composition of environmentally conditioned cleaners and the subsequent effect on aluminum/amine-cured epoxy bond integrity as measured by Tapered Double Cantilever Beam were evaluated. From this study it is observed that moisture content increases for those cleaners containing polar compounds. Non-volatile residue content increases as stabilizers are depleted and the chemical compound limonene is oxidized. A change in aluminum/ amine-cured epoxy bond fracture toughness is observed as some of these cleaners age with increases in moisture and NVR content.

Biegert, L. L.↗

NASA NTRS2001

Method of Preparing Polymers with Low Melt Viscosity

This invention is an improvement in standard polymerizations procedures, i.e., addition-type and step-growth type polymerizations, wherein monomers are reacted to form a growing polymer chain. The improvement includes employing an effective amount of a trifunctional monomer (such as a trifunctional amine anhydride, or phenol) in the polymerization procedure to form a mixture of polymeric materials consisting of branced polymers, star-shaped polymers, and linear polymers. This mixture of polymeric materials has a lower melt temperature and a lower melt viscosity than corresponding linear polymeric materials of equivalent molecular weight.

Jensen, Brian J.↗

NASA NTRS2002

PMR-15/Layered Silicate Nanocomposites For Improved Thermal Stability And Mechanical Properties

Montmorillonite clay was organically modified by co-exchange of an aromatic diamine and a primary alkyl amine. The clay was dispersed into a PMR (Polymerization of Monomer Reactants)-15 matrix and the glass transition temperature and thermal oxidative stability of the resulting nanocomposites were evaluated. PMR-15/ silicate nanocomposites were also investigated as a matrix material for carbon fabric reinforced composites. Dispersion of the organically modified silicate into the PMR-15 matrix enhanced the thermal oxidative stability, the flexural strength, flexural modulus, and interlaminar shear strength of the polymer matrix composite.

Campbell, Sandi↗

NASA NTRS1999

Tholins: Can They Provide a Substrate, Carbon and Nitrogen for Plant Production?

Tholin is a word coined to describe the entire class of complex organic solids produced in laboratory experiments where pre-biotic gaseous chemicals are subject to bombardment by high energy. The atomic composition of Titan tholin produced from 10 percent CH4 and 90 percent N2 in a simulation of Titan atmosphere irradiated by charged particles trapped in the magnetosphere of Saturn gave 67 percent C and 33 percent N. Hydrolysis of Titan tholin with 6N HCl produced a racemic mixture of biological and non-biological amino acids that was confirmed by GC/MS. Other tholins, that revealed the presence of amino acids, were UV tholin produced under possible primitive Earth conditions by irradiation of a mixture of gases (CH4, C2H6, NH3, H2S and liquid H2O) with long-wavelength ultraviolet light, representing the most abundant useful energy source for prebiological organic synthesis; Spark tholin in a crude simulation of Jupiter atmosphere using electrical discharge through a mixture of CH4, NH3, and H2O vapor. Pyrolytic GC/MS of Titan tholin produced more than one hundred organic compounds including saturated and unsaturated aliphatic hydrocarbons, substituted polycyclic aromatics, nitriles, amines, pyrroles, pyrazines, pyridines, pyrimidines, and the purine, adenine. Similar rich pyrolytic products were obtained with UV as well as Spark tholins. A range of two to four ring PAHs (Polycyclic Aromatic Hydrocarbons) in Spark as well as Titan tholins, some with one to four alkylation sites, were identified by two-step laser desorption/multiphoton ionization mass spectrometry and also confirmed by the synchronous fluorescence technique. Previous studies have demonstrated the potential for use of tholins as a source of carbon and energy by microbes. This paper describes studies that evaluate the potential for using different types of tholins as (a) a substrate for growing plants and (b) a source of carbon and nitrogen for plants. The data are interpreted in terms of the potential for using such tholins to grow plants for food in extraterrestrial habitats and also to speculate on the possibilities of abiotic evolution of plants.

Wignarajah, Kanapathipillai↗