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At least 37 records · Page 2

Peptide nucleic acids rather than RNA may have been the first genetic molecule

Numerous problems exist with the current thinking of RNA as the first genetic material. No plausible prebiotic processes have yet been demonstrated to produce the nucleosides or nucleotides or for efficient two-way nonenzymatic replication. Peptide nucleic acid (PNA) is a promising precursor to RNA, consisting of N-(2-aminoethyl)glycine (AEG) and the adenine, uracil, guanine, and cytosine-N-acetic acids. However, PNA has not yet been demonstrated to be prebiotic. We show here that AEG is produced directly in electric discharge reactions from CH(4), N(2), NH(3), and H(2)O. Electric discharges also produce ethylenediamine, as do NH(4)CN polymerizations. AEG is produced from the robust Strecker synthesis with ethylenediamine. The NH(4)CN polymerization in the presence of glycine leads to the adenine and guanine-N(9)-acetic acids, and the cytosine and uracil-N(1)-acetic acids are produced in high yield from the reaction of cyanoacetaldehyde with hydantoic acid, rather than urea. Preliminary experiments suggest that AEG may polymerize rapidly at 100 degrees C to give the polypeptide backbone of PNA. The ease of synthesis of the components of PNA and possibility of polymerization of AEG reinforce the possibility that PNA may have been the first genetic material.

NASA Discipline Exobiology↗

Chiral Selectivity as a Bridge to Homochirality

In abiotic reactions, equal mixtures of L- and D- amino acid enantiomers are produced unless conditions that favor one enantiomer over the other are present. Understanding how the transition from racemic, abiotic chemistry to homochiral polymers used in proteins occurred is fundamental to our understanding of the origins of life on Earth and the search for signs of life elsewhere, but this transition is still poorly understood. We have begun investigations into whether enantiopure amino acid pools are a necessary condition, or if the polymerization process itself can impart some added degree of stereoselectivity. More specifically, we are exploring the polymerization behavior of chiral amino acids to determine if they show a preference for homochiral or heterochiral polymerization. We are also determining the effects of different amino acid chiral ratios (L greater than D) to determine at what level of enantiomeric enrichment homochiral peptides become predominant. These data will allow us to evaluate the plausibility of homochiral polymers arising by known abiotic mechanisms.

Burton, A. S.↗

Effect of Branching on Rod-coil Polyimides as Membrane Materials for Lithium Polymer Batteries

This paper describes a series of rod-coil block co-polymers that produce easy to fabricate, dimensionally stable films with good ionic conductivity down to room temperature for use as electrolytes for lithium polymer batteries. The polymers consist of short, rigid rod polyimide segments, alternating with flexible, polyalkylene oxide coil segments. The highly incompatible rods and coils should phase separate, especially in the presence of lithium ions. The coil phase would allow for conduction of lithium ions, while the rigid rod phase would provide a high degree of dimensional stability. An optimization study was carried out to study the effect of four variables (degree of branching, formulated molecular weight, polymerization solvent and lithium salt concentration) on ionic conductivity, glass transition temperature and dimensional stability in this system.

Meador, Mary Ann B.↗

New Anti-Corrosive Coatings with Resin-Bonded Polyaniline and Related Electroactive Groups

It is already known that polyaniline (an electroactive polymer) functions as a corrosion inhibitor for steel and in view of the fact that it is known to perform in the presence of hydrochloric acid, it has been considered likely that it may be useful to NASA for protecting launch structures at KSC which are exposed to not only continual ocean-side salt spray but also to hydrochloric acid at the times that solid-fuel boosters are fired. The currently used zinc-rich silicate-bonded coating is not wholly protective against the hydrochloric acid. Water pollution from zinc salts is another concern. Other earlier and concurrent NASA sponsored projects have been focussed on polyaniline specifically. Our project, administered for NASA by Dr. K. Thompson of KSC and these more-specifically polyaniline-related projects are included in a CRADA coordinated by Dr. F. Via of Akzo Nobel. A parallel project at Polytechnic under Prof K. Levon concentrated more specifically on polyaniline with various dopants. Our exploratory project reported herein was aimed at broadening the range of such corrosion inhibitors, to give protective paint compounders a wider latitude for adding corrosion inhibitors having polyaniline-like performance, and thus we diverged in several probing directions from polyaniline. Our working hypothesis was that physical variants of polyaniline, such as supported formulations on pigments or carriers, and chemical variants of polyaniline, including those having no electroconductive character, may have enhanced anticorrosion activity. We also hypothesized that small (non-polymeric) molecules having structures related to those occurring in polyaniline, may be active as corrosion inhibitors. We did preliminary testing, using an ASTM salt spray method at a nearby commercial paint testing laboratory. Our most interesting findings were that a non-electroconductive meta-isomer of polyaniline showed some corrosion activity, suggesting that the features of the polyaniline molecule associated with conductivity are not necessary for the anticorrosion action. Also, signtficantly, small molecular weight aromatic diamines and diimines resembling the reduced and the oxidized repeating unit in polyaniline showed an interesting degree of anticorrosive activity, suggesting that the polymeric feature of polyaniline is not necessary for anticorrosion action.

Weil, Edward D.↗

Improving Silicon Carbide/Silicon Nitride Fibers

Experiments described in report indicate properties of silicon carbide/silicon nitride fibers change significantly with modifications of monomeric precursors. Monomers polymerized by heating to temperatures above 500 degree C. Fibers drawn from resin melt under stream of dry nitrogen, cured in environmental chamber at 100 degree C and 95 percent relative humidity until unmeltable, then placed under tension and pyrolyzed at 1,200 to 1,500 degree C to produce inorganic silicon carbide/silicon nitride fibers. Allows possibility of creating improved silicon carbide/silicon nitride fibers, replacing graphite fibers in composite materials requiring high electrical resistance and thermal stability.

Crouse, David J.↗

Efficient oligomerization of negatively-charged beta-amino acids at -20 degrees C

This paper describes a procedure, known as eutectic concentration, used to concentrate an aqueous solution by cooling. Using a water-soluble carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, the researchers were able to accelerate the rate of polymerization of beta-amino acids when the solution was cooled to -20 degrees C. Different temperatures and solution concentrations were investigated to determine which gave the most efficient rates of polymerization. The effect of sodium chloride on the products of the reaction was also studied.

Non-NASA Center↗

Preparation of Perfluorinated Imidoylamidoxime Polymers

Perfluorinated imidoylamidoxime polymers with excellent resistance to heat, chemicals and solvents are prepared by condensing a perfluorinated nitrile with a perfluorinated amidoxime in vacuum or inert atmosphere from 20 degrees to 70 degrees C. When both reactants are difunctional, oligomeric or polymeric products are obtained. After cyclization of imidoylamidoxime groups to 1,2,4-oxadiazole linkages, process yields highly resistant elastomers. Competing side reactions are inhibited by low processing temperature.

Rosser, R. W.↗

The growth of zeolites A, X and mordenite in space

Zeolites are a class of crystalline aluminosilicate materials that form the backbone of the chemical process industry worldwide. They are used primarily as adsorbents and catalysts and support to a significant extent the positive balance of trade realized by the chemical industry in the United States (around $19 billion in 1991). The magnitude of their efforts can be appreciated when one realizes that since their introduction as 'cracking catalysts' in the early 1960's, they have saved the equivalent of 60 percent of the total oil production from Alaska's North Slope. Thus the performance of zeolite catalysts can have a profound effect on the U.S. economy. It is estimated that a 1 percent increase in yield of the gasoline fraction per barrel of oil would represent a savings of 22 million barrels of crude oil per year, representing a reduction of $400 million in the United States' balance of payments. Thus any activity that results in improvement in zeolite catalyst performance is of significant scientific and industrial interest. In addition, due to their 'stability,' uniformity, and, within limits, their 'engineerable' structures, zeolites are being tested as potential adsorbents to purify gases and liquids at the parts-per-billion levels needed in today's electronic, biomedical, and biotechnology industries and for the environment. Other exotic applications, such as host materials for quantum-confined semiconductor atomic arrays, are also being investigated. Because of the importance of this class of material, extensive efforts have been made to characterize their structures and to understand their nucleation and growth mechanisms, so as to be able to custom-make zeolites for a desired application. To date, both the nucleation mechanics and chemistry (such as what are the 'key' nutrients) are, as yet, still unknown for many, if not all, systems. The problem is compounded because there is usually a 'gel' phase present that is assumed to control the degree of supersaturation, and this gel undergoes a continuous 'polymerization' type reaction during nucleation and growth. Generally, for structure characterization and diffusion studies, which are useful in evaluating zeolites for improving yield in petroleum refining as well as for many of the proposed new applications (e.g., catalytic membranes, molecular electronics, chemical sensors) large zeolites (greater than 100 to 1000 times normal size) with minimum lattice defects are desired. Presently, the lack of understanding of zeolite nucleation and growth precludes the custom design of zeolites for these or other uses. It was hypothesized that the microgravity levels achieved in an orbiting spacecraft could help to isolate the possible effects of natural convection (which affects defect formation) and minimize sedimentation, which occurs since zeolites are twice as dense as the solution from which they are formed. This was expected to promote larger crystals by allowing growing crystals a longer residence time in a high-concentration nutrient field. Thus it was hypothesized that the microgravity environment of Earth orbit would allow the growth of large, more defect-free zeolite crystals in high yield.

Sacco, Albert, Jr.↗

Ion Beam Sputtered Coatings of Bioglass

The ion beam sputtering technique available at the NASA-Lewis was used to apply coatings of bioglass to ceramic, metallic, and polymeric substrates. Experiments in vivo and in vitro described investigate these coatings. Some degree of substrate masking was obtained in all samples although stability and reactivity equivalent to bulk bioglass was not observed in all coated samples. Some degree of stability was seen in all coated samples that were reacted in vitro. Both metallic and ceramic substrates coated in this manner failed to show significantly improved coatings over those obtained with existing techniques. Implantation of the coated ceramic substrate samples in bone gave no definite bonding as seen with bulk glass; however, partial and patchy bonding was seen. Polymeric substrates in these studies showed promise of success. The coatings applied were sufficient to mask the underlying reactive test surface and tissue adhesion of collagen to bioglass was seen. Hydrophilic, hydrophobic, charged, and uncharged polymeric surfaces were successfully coated.

Hench, Larry L.↗

The casting of semi-permeable membranes in a microgravity environment

The National Electric Company of Venezuela, C.A.D.A.F.E., is sponsoring the development of this experiment which represents Venezuela's first scientific experiment in space. The experience can be classified as an educational one which could add knowledge to the fundamental study of polymeric membranes. Presently, semi-permeable membranes are being manufactured from several different kind of polymers all over the world and specific applications have been identified in fluid separation processes such as reverse osmosis, ultrafiltration and electrodyalisis. Although, the ultrastructure of asymetric and composite membranes have been under intensive study, still there are many questions about the factors affecting this structure and their degree of correlation. Nevertheless, there is indication that the entire morphological structure of polymeric membranes could be affected by the differences in specific gravity between the cast solution and the coagulation liquid, normally used in the membranes preparation process. The casting of semi-permeable membranes in space might help to identify the effect of gravity upon the structure of these membranes. It is important to recognize that the casting process involves changes of states (liquid-gas, liquid-solid) and that in a micro gravity environment, there will be a reduction on buoyancy-driven natural convection and density gradients

Ivan Vera↗

Influence of thread construction on strength of ceramic sewing threads

The effects of two thread construction variables, yarn twist and polymeric sizing, on break strength were obtained for a silica thread and two types of aluminoborosilicate (ABS) threads at temperatures ranging from 23 C to 1200 C. It was shown that increasing the degree of twist for the silica thread produced an optimum twist level until all the yarn finish was removed. The break strength of both ABS threads was inversely proportional to the degree of twist caused by increased filament breakage with increasing twist that was controlled by the gradual removal of the polymeric processing aids. At elevated temperatures, above 950 C, strength loss was observed for both ABS threads because of the presence of a glass phase that softens and causes fiber deformation. This was not observed for the silica thread at similar test temperatures because of the higher viscosity of the pure silica glass phase.

Sawko, Paul M.↗

Moisture resistant and anti-reflection optical coatings produced by plasma polymerization of organic compounds

The need for protective coatings on critical optical surfaces, such as halide crystal windows or lenses used in spectroscopy, has long been recognized. It has been demonstrated that thin, one micron, organic coatings produced by polymerization of flourinated monomers in low temperature gas discharge (plasma) exhibit very high degrees of moisture resistence, e.g., hundreds of hours protection for cesium iodide vs. minutes before degradation sets in for untreated surfaces. The index of refraction of these coatings is intermediate between that of the halide substrate and air, a condition for anti-reflection, another desirable property of optical coatings. Thus, the organic coatings not only offer protection, but improved transmittance as well. The polymer coating is non-absorbing over the range 0.4 to 40 microns with an exception at 8.0 microns, the expected absorption for C-F bonds.

Hollahan, J. R.↗

Improved Fire-Resistant Resins for Laminates

Fire-resistant resins for fabricating laminates with inorganic fibers, especially graphite fibers, are formed from bisimides containing main-chain phosphorus and olefinic end groups. Bisimides are thermally polymerized to form resins and laminates virtually imcombustible in pure oxygen at 300 degrees C. New resins are suitable for many applications requiring good adhesion and excellent resistance to heat, fire, solvents and chemicals.

Fohlen, G. M.↗

Bisimide amine cured epoxy /IME/ resins and composites. II - Ten-degree off-axis tensile and shear properties of Celion 6000/IME composites

Bisimide amines (BIAs), which are presently used as curing agents in a state-of-the-art epoxy resin, are oligomeric and polymeric mixtures. A series of composites consisting of the novel BIA-cured epoxy resin reinforced with Celion 6000 graphite fibers were fabricated and evaluated, and the ten-degree, off-axis uniaxial tensile and shear properties of these composites were determined. The use of the intralaminar shear strain-to-failure was used in the calculation of resin shear strain-to-failure. Study results indicate that several of these novel composite systems exhibit shear strain properties that are superior to those of the control composite system of the present experiments, which employed a sulfone curing agent.

Scola, D. A.↗

A Rapid Survey of the Compatibility of Selected Seal Materials with Conventional and Semi-Synthetic JP-8

Since the synthesis of a liquid hydrocarbon fuel from coal by Franz Fischer and Hans Tropsch in 1923, there has been cyclic interest in developing this fuel for military and commercial applications. In recent years the U.S. Department of Defense has taken interest in producing a unified battlespace fuel using the Fischer Tropsch (FT) process for a variety of reasons including cost, quality, and logistics. In the past year there has been a particular emphasis on moving quickly to demonstrate that an FT fuel can be used in the form of a blend with conventional petroleum-derived jet fuel. The initial objective is to employ this semi-synthetic fuel with blend ratios as high as 50 percent FT with longer range goals to use even high blend ratios and ultimately a fully synthetic jet fuel. A significant concern associated with the use of a semi-synthetic jet fuel with high FT blend ratios is the effect these low aromatic fuels will have on fuel-wetted polymeric materials, most notably seals and sealants. These materials typically swell and soften to some degree when exposed to jet fuel and the aromatic content of these fuels contribute to this effect. Semi-synthetic jet fuels with very low aromatic contents may cause seals and sealants to shrink and harden leading to acute or chronic failure. Unfortunately, most of the material qualification tests are more concerned with excessive swelling than shrinkage and there is little guidance offered as to an acceptable level of shrinkage or other changes in physical properties related to low aromatic content. Given the pressing need for guidance data, a program was developed to rapidly survey the volume swell of selected fuel-wetted materials in a range of conventional and semi-synthetic jet fuels and through a statistical analysis to make a determination as to whether there was a basis to be concerned about using fuels with FT blend ratios as high as 50 percent. Concurrent with this analysis data was obtained as to the composition of the fuel absorbed in fuel-wetted materials through the use of GC-MS analysis of swollen samples as well as other supporting data. In this presentation the authors will present a summary of the results of the volume swell and fuel absorbed by selected O-rings and sealants as well as a description of the measurement protocols developed for this program.

Graham, John L.↗

Vacuum Baking To Remove Volatile Materials

Outgassing reduced in some but not all nonmetallic materials. Eleven polymeric materials tested by determining outgassing species as temperature of conditioned and unconditioned materials raised to 300 degrees C. Conditioning process consisted of vacuum bake for 24 hours at 80 degrees C in addition to usual cure. Baking did not change residual gas percentage of water molecules.

Muscari, J. A.↗

Polyenamines for Films, Coatings, and Adhesives

Easy process makes polymers with good mechanical properties. Synthesis involves Michael-type addition polymerization of two diacetylenic diketones, with various aromatic diamines in m-cresol at 60 to 130 degrees C. Technique provides synthetic route to high-molecular-weight polyenamines with moderate thermal stability and good mechanical properties. Polyenamines produced exhibit potential for use as films, coatings, adhesives, molding compounds, and composite matrices.

Hergenrother, Paul M.↗

Plasma polymerization of an ethylene-nitrogen gas mixture

A procedure has been developed whereby nitrogen can be incorporated into an organic film from an ethylene-nitrogen gas mixture using an internal electrode capacitively coupled radio frequency reactor. The presence of nitrogen has been shown directly by infrared transmittance spectra and electron spectroscopic chemical analysis data, and further indirect evidence was provided by dielectric measurements and by the reverse osmosis properties of the film. Preparation of a nitrogen containing film did not require vapor from an organic nitrogen containing liquid monomer. Some control over the bonding and stoichiometry of the polymer film was provided by the added degree of freedom of the nitrogen partial pressure in the gas mixture. This new parameter strongly affected the dielectric properties of the plasma polymerized film and could affect the reverse osmosis behavior.

Hudis, M.↗