SEARCH · Engineering Papers
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Explore the source record for details and available documents.
The prebiotic synthesis of imidazole-4-acetaldehyde and imidazole-4-glycol from erythrose and formamidine has been demonstrated as well as the prebiotic synthesis of imidazole-4-ethanol and imidazole-4-glycol from erythrose, formaldehyde, and ammonia. The maximum yields of imidazole-4-acetaldehyde, imidazole-4-ethanol, and imidazole-4-glycol obtained in these reactions are 1.6, 5.4, and 6.8 percent respectively, based on the erythrose. Imidazole-4-acetaldehyde would have been converted to histidine on the primitive earth by a Strecker synthesis, and several prebiotic reactions would convert imidazole-4-glycol and imidazole-4-ethanol to imidazole-4-acetaldehyde.
Development of two models for the condensation of nucleotides under possibly prebiotic conditions. In the first of these models this type of reaction is promoted by the presence of imidazole and substituted imidazole compounds. The second model involves the condensation of mononucleotides with cyanamide in the presence and absence of a prototemplate such as polyornithine. A tentative mechanism for the role of imidazole catalysis in phosphodiester bond formation between adjacent TMP molecules is suggested.
The structures, the harmonic frequencies, and the energies of Fe2+(H2O)n(imid)m and Ni2+(H2O)n(imid)m complexes are computed using density functional theory with the B3LYP functional. A CSOV analysis shows that the bonding is mostly electrostatic in nature. Imidazole forms a stronger bond than water with both metal dications due to its larger dipole moment and polarizability. The reactions for the exchange of one water molecule by one imidazole are exothermic and up to six water molecules can be replaced by imidazoles. The trends are very similar for both metals with the displacement reactions being slightly more favorable for Ni(2+).
Results are reported on an unsuccessful 6-cm search for the heterocyclic carbon ring molecules furan and imidazole. Upper limits in brightness temperature of 0.25 K or less are found for furan in 11 galactic sources, and of less than 0.1 K for imidazole in Sgr A and Sgr B2.
Films adhere well to some substrates, provide smooth surfaces, and facilitate release from molds. Thin films of thermoplastic poly(arylene ether imidazole)s (PAEI's) particularly suitable for use as surface modifiers for graphite/epoxy or graphite/bismaleimide composite panels. Molecule of PAEI includes imidazole groups along its backbone that co-cure with epoxies or bismaleimides during processing. Films thermally stable and resistant to bombardment by energetic electrons.
A toughened epoxy was prepared by reacting an epoxy resin with a poly(arylene ether-co-imidazole)s (PAEI). The epoxy resin comprises N,N,N',N'tetraglycidyl-4,4'- methylenebisbenzenamine and 4-aminophenyl sulfone. The PAEI was prepared by reacting an aromatic bisphenol, a bisphenol imidazole, and an activated aromatic dihalide or dinitro compound in the presence of potassium carbonate in a polar aprotic solvent at an elevated temperature. The epoxies which were modified with these particular PAEI's showed a significant increase in toughness with only a 10 weight percent loading of the PAEI into the epoxy. These toughened epoxies were used to prepare composites and molded parts.
Films of thermoplastic poly(arylene ether imidazole)s (PAEIs) are used as surface modifiers for neat resin panels and composite resin panels. The PAEI polymer contains imidazole groups along the backbone which co-cure, i.e., react chemically, with epoxies or bismaleimides during processing and thereby provide excellent adhesion between the PAEI film and an epoxy or bismaleimide neat resin or composite resin facesheet. The film provides good adhesion and a smooth surface to the finished part and acts as a release agent from the mold. The as-processed integral structures have very smooth (specular) surfaces, and since the film releases readily from a glass mold, no release agent is necessary. The PAEI film is thermally stable, resistant to electron radiation, and adheres tenaciously to the facesheet. The film maintains good adhesion even after thermal cycling from room temperature to approximately -196 C.
Films of thermoplastic poly(arylene ether imidazole)s (PAEI)s are used as surface modifiers for neat resin panels and composite resin panels. The PAEI polymer contains imidazole groups along the backbone which co-cure, i.e., react chemically, with epoxies or bismaleimides during processing and thereby provide excellent adhesion between the PAEI film and an epoxy or bismaleimide neat resin or composite resin facesheet. The film provides good adhesion and a smooth surface to the finished part and acts as a release agent from the mold. The as-processed integral structures have very smooth (specular) surfaces, and since the film releases readily from a glass mold, no release agent is necessary. The PAEI film is thermally stable, resistant to electron radiation, and adheres tenaciously to the facesheet. The film maintains good adhesion even after thermal cycling from room temperature to .about. -196.degree. C.
As part of a program to develop high-temperature high-performance structural resins for aerospace applications, the chemistry and properties of new poly(arylene ether imidazoles) were investigated. The polymers were prepared by the nucleophilic displacement reaction of aromatic bis(imidazolephenols) with activated aromatic difluoro compounds. The amorphous thermoplastic polymers exhibited glass transition temperatures from 230 to 301 C, inherent viscosities from 0.46 to 1.46 dL/g, and number-average molecular weights as high as 59,300 g/mole. The polymers exhibit good toughness, adhesive, composite, and film properties. The chemical, physical, and mechanical properties of these materials are discussed.
A series of novel NLO (chromophores) imidazole chromophores containing tricyanovinyl acceptor coupled with thiophene have been developed.
Two new classes of two-photon absorbing Y-shaped molecules have been developed to possess an imidazole-thiazole core and a stilbene-type conjugation pathway with either nitro or sulfonyl as terminal electron-accepting group.
Condensation reactions in cyanamide, 4-amino-5-imidazole-carboxamide and cyanamide, imidazole systems under dehydrating conditions at moderate temperatures (60 to 100 deg C) were investigated. The cyanamide, imidazole system was used for synthesis of palmitoylglycerols from ammonium palmitate and glycerol. With the addition of deoxythymidine to the former system, P1, P2-dideoxythymidine 5 prime-phosphate was obtained; the same cyanamide, 4-amino-5-imidazole-carboxamide system was used to synthesize deoxythymidine oligonucleotides using deoxythymidine 5 prime-phosphate and deoxythymidine 5 prime-triphosphate, and peptides using glycine, phenylalanine or isoleucine with adenosine 5 prime-triphosphate. The pH requirements for these reactions make their prebiotic significance questionable; however, it is conceivable that they could occur in stable pockets of low interlayer acidity in a clay such as montmorillonite.
Polyimidazoles (PI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl) imidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as N,N-dimethyl acetamide, sulfolane, N-methylpyrrolidinone, dimethylsulfoxide, or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl) imidazole monomers are prepared by reacting an aromatic aldehyde with a dimethoxybenzil or by reacting an aromatic dialdehyde with a methoxybenzil in the presence of ammonium acetate. The di(methoxyphenyl) imidazole is subsequently treated with aqueous hydrobromic acid to give the di(hydroxphenyl) imidazole monomer. This synthetic route has provided high molecular weight PI of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides and dinitro compounds.
Polyimidazoles (Pl) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl)imidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as N,N-dimethylacetamide, sulfolane, N-methylpyrroldinone, dimethylsulfoxide, or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperature under nitrogen. The di(hydroxyphenyl)imidazole monomers are prepared by reacting an aromatic aldehyde with a dimethoxybenzil or by reacting an aromatic dialdehyde with a methoxybenzil in the presence of ammonium acetate. The di(methoxyphenyl)imidazole is subsequently treated with aqueous hydrobromic acid to give the di(hydroxyphenyl)imidazole monomer. This synthetic route has provided high molecular weight Pl of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides and dinitro compounds.
Conjugated polyenes, and polyesters containing phthalocyanine in their backbone, were synthesized. These polymers were characterized by chemical analysis, thermogravimetric analysis, spectral analysis, and X-ray diffraction studies for crystallinity, as well as for their film-forming capability and gas/polymer interactions. Most of the polymers were relatively insensitive to water vapor up to 50 percent relative humidity, but the polyester/phthalocyanine (iron) polymer was relatively insensitive up to 100 percent RH. On the other hand, poly(p-dimethylaminophenylacetylene) was too conductive at 100 percent RH. Of the gases tested, the only ones that gave any evidence of interacting with the polymers were SO2, NOx, HCN and NH3. Poly(imidazole)/thiophene responded to each of these gases at all relative humidities, while the other polymers gave varying response, depending upon the RH. Thus, since most of these gases were electron-accepting, the electron-donating character of poly(imidazole)/thiophene substantiates the concept of electronegativity being the operating principle for interaction effects. Of the six polymers prepared, poly(imidazole)/thiophene first showed a very good response to smoldering cotton, but it later became nonresponsive; presumably due to oxidation effects.
Imidazole catalysis of phenylalanyl transfer from phenylalanine adenylate to hydroxyl groups of homopolyribonucleotides is studied as a possible chemical model of biochemical aminoacylation of transfer RNA (tRNA). The effect of pH on imidazole-catalyzed transfer of phenylalanyl residues to poly(U) and poly(A) double helix strands, the number of peptide linkages and their lability to base and neutral hydroxylamine, and the nature of adenylate condensation products are investigated. The chemical model entertained exhibits a constraint by not acylating the hydroxyl groups of polyribonucleotides in a double helix. The constraint is consistent with selective biochemical aminoacylation at the tRNA terminus. Interest in imidazole as a model of histidine residue in protoenzymes participating in prebiotic aminoacyl transfer to polyribonucleotides, and in rendering the tRNA a more efficient adaptor, is indicated.
The autocondensation of the glyceroyl thioester, S-glyceroyl-ethane-thiol, yielded olioglyceric acid. The rates of autocondensation and hydrolysis of the thioester increased from pH 6.5 to pH 7.5 in 2,6-lutidine and imidazole buffers. Autocondensation and hydrolysis were much more rapid in imidazole buffers as compared to 2,6-lutidine and phosphate buffers. The efficiency of ester bond synthesis was about 20% for 40 mM S-glyceroyl-ethane-thiol in 2,6-lutidine and imidazole buffers near neutral pH. The size and yield of the olioglyceric acid products increased when the concentration of the thioester was increased. The relationship of these results to prebiotic polymer synthesis is discussed.