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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
NASA NTRS1987

Semi-2-interpenetrating networks of high temperature systems

A semi-2-interpenetrating network of improved qualities which is prepared by combining a linear polymer and a cross-linkable oligomer having identical repeating units is developed. Polymers have been combined in the past into interpenetrating networks in order to gain useful properties from the combination of materials. However, previous semi-interpenetrating networks have only been formed using polymers having different repeating units. This method provides a semi-2-interpenetrating network of improved strength, adhesion, and processability.

Egli, Annmarie O.↗
NASA NTRS1986

Kinetics of the hydrolysis of guanosine 5'-phospho-2-methylimidazolide

The hydrolysis kinetics of guanosine 5'-phospho-2-methylimidazolide (2-MeImpG) in aqueous buffered solutions of various pH's was studied at 75 and 37 C, using spectrophotometric and HPLC techniques. The hydrolysis was found to be very slow even at low pH. At 75 C and pH at or below l.0, two kinetic processes were observed: the more rapid one was attributed to the hydrolysis of the phosphoimidazolide P-N bond; the second, much slower one, was attributed to the cleavage of the glycosidic bond. It is noted that the P-N hydrolysis in phosphoimidazolides is very slow compared to other phosphoramidates, and that this might be one of the reasons why the phosphoimidazolides showed an extraordinary ability to form long oligomers under template-directed conditions.

Kanavarioti, Anastassia↗
NASA NTRS1987

Kinetic analysis of the template effect in ribooligoguanylate elongation

The paper presents kinetic studies on the reaction of elongation of the 3-prime-5-prime-linked ribooligoguanylates with guanosine 5-prime-phospho-2-methylimidazolide (2-MelmpG) in the presence or absence of a complementary template, the polycytidylic acid. In the absence of poly(C), the reaction leads to three isomeric oligomers that are elongated by one monomer unit: the 3-prime-5-prime linked, the 2-prime-5-prime linked, and the pyrophosphate, formed in a ratio of 1:2:5. In the presence of the template, the reaction is 20-fold faster and yields products (n + 1), (n + 2), (n + 3), etc., as long as 2-MelmpG is available. The formation of the natural, 3-prime-5-prime-linked isomer, is enhanced selectively by 140-fold at 37 C, and its relative yield increases with decreasing temperature.

Kanavarioti, Anastassia↗
NASA NTRS1987

Nucleic acid-like structures. II - Polynucleotide analogues as possible primitive precursors of nucleic acids

Activated derivatives of purine-containing deoxynucleoside- diphosphates spontaneously oligomerize to produce pyrophosphate- linked oligodeoxynucleotide analogs. These analogs are of potential interest as models of primitive, polynucleotide precursors. The efficiency of oligomerization (ImpdGpIm and ImpdApIm much greater than ImpdIpIm) appears to reflect a combination of stacking forces and the specific geometric orientations of the stacked units. Under favorable conditions, chain lengths greater than 20 have been obtained for oligomers containing pdGp in the absence of a template. In the presence of a complementary template, the activated derivatives of pdGp and pdAp oligomerize much more extensively. An acyclo-analog of G has also been shown to undergo template-directed oligomerization on poly(C). These observations suggest the possibility that primitive information transfer might have evolved in much simpler systems and that this function was taken over by polynucleotides at a later stage in evolution.

Schwartz, Alan W.↗
NASA NTRS1989

Acetylene-Terminated Aspartimides And Derived Resins

New polymers and derived blends exhibit improved processability and properties. New toughened epoxies exhibit excellent properties, but use temperatures limited. Bismaleimide resins are some base materials formulated to develop materials having moderate use temperatures. Work conducted on use of acetylenic (ethynyl) group to cross-link and extend chains of oligomers and polymers to obtain materials to perform at higher temperatures. Extended to include acetylene-terminated aspartimides (ATA's).

Hergenrother, Paul M.↗
NASA NTRS1988

Addition polymers from 1,4,5,8-tetrahydro-1,4;5,8-diepoxyanthracene and Bis-dienes. 2: Evidence for thermal dehydration occurring in the cure process

Diels-Alder cycloaddition copolymers from 1,4,5,8-tetrahydro-1,4;5,8-diepoxyanthracene and anthracene end-capped polyimide oligomers appear, by thermogravimetric analysis (TGA), to undergo dehydration at elevated temperatures. This would produce thermally stable pentiptycene units along the polymer backbone, and render the polymers incapable of unzipping through a retro-Diels-Alder pathway. High resolution solid 13C nuclear magnetic resonance (NMR) of one formulation of the polymer system before and after heating at elevated temperatures, shows this to indeed be the case. NMR spectra of solid samples of the polymer before and after heating correlated well with those of the parent pentiptycene model compound before and after acid-catalyzed dehydration. Isothermal gravimetric analyses and viscosities of the polymer before and after heat treatment support dehydration as a mechanism for the cure reaction.

Meador, Mary Ann B.↗
NASA NTRS1989

Composites of vinyl polystyrylpyridine/bismaleimide-aliphatic ether copolymers

An aliphatic ether bismaleimide was prepared and coreacted with a polyvinylstyrylpyridine (VPSP) oligomer. Studies showed that a controlled ratio of aliphatic to aromatic units in the polymer backbone improved both processibility and interlaminar shear properties for the carbon-fiber composite system. This modified resin was readily soluble in tetrahydrofuran, allowing for better fiber impregnation and thus enhancing adhesive properties and reproducibility. DSC studies have shown a lower cure temperature for the copolymer than for the neat aliphatic bismaleimide, and a glass transition temperature of 260 C, which is more than adequate for most applications. Limited measurements indicated an improvement in toughness (impact resistance).

Heimbuch, Alvin H.↗
NASA NTRS1989

Mineral catalysis of the formation of the phosphodiester bond in aqueous solution - The possible role of montmorillonite clays

The possible role of montmorillonite clays in the spontaneous formation on the primitive earth of the phosphodiester bond in the presence of water was investigated in experiments measuring the binding of various nucleosides and nucleotides with Na(+)-montmorillonite 22A and the reactions of these compounds with a water-soluble carbodiimide. It was found that, at neutral pH, adenine derivatives bind stronger than the corresponding uracil derivatives, consistent with the protonation of the adenine by the acidic clay surface and a cationic binding of the protonated ring to the anionic clay surface. The reaction of the 5-prime-AMP with carbodiimide resulted in the formation of 2-prime,5-prime-pApA (18.9 percent), 3-prime,5-prime-pApA (11 percent), and AppA (4.8 percent). The yields of these oligomers obtained when poly(U) was used in place of the clay were 15.5 percent, 3.7 percent, and 14.9 percent AppA, respectively.

Ferris, James P.↗
NASA NTRS1989

Oligomerization of deoxynucleoside-biphosphate dimers - Template and linkage specificity

The oligomerization of the activated 3-prime-5-prime pyrophosphate-linked dimer, pdAppdAp, is presently noted to be selectively favored by a poly(U) template over the 3-prime-3-prime and 5-prime-5-prime linked dimers. Both overall yields and the production of the longest oligomers were markedly stimulated by poly(U)'s presence; in its absence, the 5-prime-5-prime linked dimer became the most reactive, yielding chains of the order of 60 monomer-unit lengths. Remarkable self-organization properties are noted for the 5-prime-5-prime dimer of pdAp.

Visscher, J.↗
NASA NTRS1990

Ethynyl-Terminated Imidothioethers And Derived Resins

New toughened epoxies exhibit excellent properties, but temperatures at which used limited. Bismaleimide resins some of base materials being formulated to develop materials used at moderate temperatures. Work conducted on use of acetylenic (ethynyl) group to cross-link and extend chains of oligomers and polymers to obtain materials that perform at high temperatures. Work extended to ethynyl-terminated imidothioethers (ETI's). Tested primarily as adhesives and composite matrices and found to have useful properties in terms of processing, resistance to high temperature, fracture toughness, and resistance to solvents. Also have desirable mechanical properties. Potentially useful for aerospace and nonaerospace applications.

Hergenrother, Paul M.↗
NASA NTRS1989

Acetylene terminated aspartimides and resins therefrom

Acetylene terminated aspartimides are prepared using two methods. In the first, an amino-substituted aromatic acetylene is reacted with an aromatic bismaleimide in a solvent of glacial acetic acid and/or m-cresol. In the second method, an aromatic diamine is reacted with an ethynyl containing maleimide, such an N-(3-ethynyl phenyl) maleimide, in a solvent of glacial acetic acid and/or m-cresol. In addition, acetylene terminated aspartimides are blended with various acetylene terminated oligomers and polymers to yield composite materials exhibiting improved mechanical properties.

Hergenrother, Paul M.↗
NASA NTRS1989

Condensation polyimides

Polyimides belong to a class of polymers known as polyheterocyclics. Unlike most other high temperature polymers, polyimides can be prepared from a variety of inexpensive monomers by several synthetic routes. The glass transition and crystalline melt temperature, thermooxidative stability, toughness, dielectric constant, coefficient of thermal expansion, chemical stability, mechanical performance, etc. of polyimides can be controlled within certain boundaries. This versatility has permitted the development of various forms of polyimides. These include adhesives, composite matrices, coatings, films, moldings, fibers, foams and membranes. Polyimides are synthesized through both condensation (step-polymerization) and addition (chain growth polymerization) routes. The precursor materials used in addition polyimides or imide oligomers are prepared by condensation method. High molecular weight polyimide made via polycondensation or step-growth polymerization is studied. The various synthetic routes to condensation polyimides, structure/property relationships of condensation polyimides and composite properties of condensation polyimides are all studied. The focus is on the synthesis and chemical structure/property relationships of polyimides with particular emphasis on materials for composite application.

Hergenrother, P. M.↗
NASA NTRS1988

Processable, high temperature polymers from 1,4,5,8-tetrahydro-1,4;5,8-diepoxyanthracene and bis-dienes

1,4,5,8-tetrahydro-1,4;5,8-diepoxyanthracene reacts with various anthracene end-capped polyimide oligomers to form Diels-Alder cycloaddition copolymers. The polymers are soluble in common organic solvents, and have molecular weights of approximately 21,000 to 32,000. These resins exhibit lower weight loss in air than in nitrogen. This is suggested to be due to dehydration (loss of water ranges from 2 to 5 percent) at temperatures of 390 to 400 C to give thermooxidatively stable pentiptycene units along the polymer backbone. Because of their high softening points and good thermooxidative stability, the polymers have potential as processable, matrix resins for high temperature composite applications.

Meador, Mary Ann B.↗
NASA NTRS1989

Oligomerization reactions of deoxyribonucleotides on montmorillonite clay - The effect of mononucleotide structure on phosphodiester bond formation

The formation of oligomers from deoxynucleotides, catalyzed by Na(+)-montmorillonite, was investigated with special attention given to the effect of the monomer structure on the phosphodiester bond formation. It was found that adenine deoxynucleotides bind more strongly to montmorillonite than do the corresponding ribonucleotides and thymidine nucleotides. Tetramers of 2-prime-dpA were detected in the reaction of 2-prime-d-5-prime-AMP with a water-soluble carbodiimide EDAC in the presence of Na(+)-montmorillonite, illustrating the possible role of minerals in the formation of biopolymers on the primitive earth.

Ferris, James P.↗
NASA NTRS1989

Interpenetrating polymer networks from acetylene terminated materials

As part of a program to develop high temperature/high performance structural resins for aerospace applications, the chemistry and properties of a novel class of interpenetrating polymer networks (IPNs) were investigated. These IPNs consist of a simple diacetylenic compound (aspartimide) blended with an acetylene terminated arylene ether oligomer. Various compositional blends were prepared and thermally cured to evaluate the effect of crosslink density on resin properties. The cured IPNs exhibited glass transition temperatures ranging from 197 to 254 C depending upon the composition and cure temperature. The solvent resistance, fracture toughness and coefficient of thermal expansion of the cured blends were related to the crosslink density. Isothermal aging of neat resin moldings, adhesive and composite specimens showed a postcure effect which resulted in improved elevated temperature properties. The chemistry, physical and mechanical properties of these materials will be discussed.

Connell, J. W.↗
NASA NTRS1990

Polymerization of amino acids containing nucleotide bases

The nucleoamino acids 1-(3'-amino,3'-carboxypropyl)uracil (3) and 9-(3'-amino,3'-carboxypropyl)adenine (4) have been prepared as (L)-en-antiomers and as racemic mixtures. When 3 or 4 is suspended in water and treated with N,N'-carbon-yldiimidazole, peptides are formed in good yield. The products formed from the (L)-enantiomers are hydrolyzed to the monomeric amino acids by pronase. Attempts to improve the efficiency of these oligomerizations by including a polyuridylate template in the reaction mixture were not successful. Similarly, oligomers derived from the (L)-enantiomer of 3 did not act as templates to facilitate the oligomerization of 4.

Ben Cheikh, Azzouz↗
NASA NTRS1990

N-(3-ethynylphenyl)maleimide

Acetylene terminated aspartimides are prepared using two methods. In the first, an amino-substituted aromatic acetylene is reacted with an aromatic bismaleimide in a solvent of glacial acetic acid and/or m-cresol. In the second method, an aromatic diamine is reacted with an ethynyl containing maleimide, such as N-(3-ethynylphenyl) maleimide, in a solvent of glacial acetic acid and/or m-cresol. In addition, acetylene terminated aspartimides are blended with various acetylene terminated oligomers and polymers to yield composite materials exhibiting improved mechanical properties.

Hergenrother, Paul M.↗
NASA NTRS1990

Oligomerizations of deoxyadenosine bis-phosphates and of their 3-prime-5-prime, 3-prime-3-prime, and 5-prime-5-prime dimers - Effects of a pyrophosphate-linked, poly(T) analog

The effect of a 3-prime-5-prime pyrophosphate-linked oligomer of pTp on oligomerizations of pdAp and of its 3-prime-5-prime, 3-prime-3-prime, and 5-prime-5-prime dimers was investigated, using HPLC to separate the reaction mixtures; peak detection was by absorbance monitoring at 254 nm. It was expected that the dimers would form stable complexes with the template, with the degree of stability depending upon the internal linkage of each dimer. It was found that, although the isomers differ substantially in their oligomerization behavior in the absence of template, the analog-template catalyzes the oligomerization to about the same extent in all three cases.

Visscher, J.↗