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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 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1997

Dimerization in Highly Concentrated Solutions of Phosphoimidazolide Activated Mononucleotides

Phosphoimidazolide activated ribomononucleotides (*pN) are useful substrates for the non-enzymatic synthesis of polynucleotides. However, dilute neutral aqueous solutions of *pN typically yield small amounts of dimers and traces of polymers; most of *pN hydrolyzes to yield nucleoside 5'-monophosphate. Here we report the self-condensation of nucleoside 5'-phosphate 2- methylimidazolide (2-MeImpN with N = cytidine, uridine or guanosine) in the presence of Mg2(+) in concentrated solutions, such as might have been found in an evaporating lagoon on prebiotic Earth. The product distribution indicates that oligomerization is favored at the expense of hydrolysis. At 1.0 M, 2-MelmpU and 2-MelmpC produce about 65% of oligomers including 4% of the 3',5'-Iinked dimer. Examination of the product distribution of the three isomeric dimers in a self-condensation allows identification of reaction pathways that lead to dimer formation. Condensations in a concentrated mixture of all three nucleotides (U,C,G mixtures) is made possible by the enhanced solubility of 2-MeImpG in such mixtures. Although percent yield of intemucleotide linked dimers is enhanced as a function of initial monomer concentration, pyrophosphate dimer yields remain practically unchanged at about 20% for 2-MelmpU, 16% for 2-MeImpC and 25% of the total pyrophosphate in the U,C,G mixtures. The efficiency by which oligomers are produced in these concentrated solutions makes the evaporating lagoon scenario a potentially interesting medium for the prebiotic synthesis of dimers and short RNAs.

Kanavarioti, Anastassia↗
NASA NTRS1973

Condensation in CO2 free jet expansions. I - Dimer formation.

A theoretical and experimental investigation of the kinetics of CO2 dimer formation in the adiabatically expanding core of a free jet expansion has been carried out. The theoretical analysis is based on dimer formation by an efficient termolecular process and dimer destruction by bimolecular collisions. Account is taken of the expected variation of the specific heat ratio during the expansion and of the effective increase in the termolecular collision rate at low temperatures due to the presence of loosely bound orbiting pairs. Experimental dimer concentrations were measured mass spectrometrically by forming a molecular beam from the expanded gas mixture after the onset of molecular flow. Observed dimer concentrations, for a range of pre-expansion conditions of 400 to 900 torr pressure and room temperature, are in good agreement with the theoretical analysis, provided that account is taken of the effect of loosely bound orbiting pairs at low temperatures.

Dorfeld, W. G.↗
NASA NTRS1988

Chemistry of the CO dimer at low temperatures

Researchers conducted a series of experiments on the chlorine-catalyzed photodecomposition of O sub 3 both in the gas and in inert solvents such as CF sub 4 and CO sub 2 in the temperature range about 190 to 225 K. The liquid medium was chosen in order to minimize possible surface loss of long-lived ClO dimer, and to aid in the stabilization of transient excited intermediates. The mechanism of dimer formation was as follows: (1) Cl sub 2 + hv yields Cl + Cl; (2) Cl + O sub 3 yields ClO + O sub 2; (3) ClO + ClO yields Cl sub 2 O sub 2. The experiments were done in cooled low temperature cells, with irradiation from an Osram high pressure mercury arc, filtered to remove radiation below 325 nm. Spectral analysis was by means of a Cary Model 2200 UV spectrometer. The principal objectives were: (1) to determine the lifetime of the dimer as a function of temperature; (2) to observe spectral changes in the mixtures which could be attributed to dimer or related products; and (3) to observe chemical or photochemical reactions of the dimer.

Demore, W. B.↗
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 NTRS1992

A molecular beam mass spectrometric study of the formation and photolysis of C(lc)lO dimer

A study of the chlorine oxides present at temperatures and pressures typical of the Antarctic stratosphere was carried out. A series of low temperature flow reactors was constructed and used in conjunction with molecular beam mass spectrometric techniques to identify species and characterize their kinetic behavior at temperatures of -20 to -70 C and pressures of from 30 to 130 Torr. It was found that the gas phase chlorine-oxygen system was quite complex at low temperatures. ClO dimer was identified and found to be thermodynamically very stable under stratospheric conditions. It was also found that any system which contained ClO also contained a larger oxide. The oxide was identified as Cl2O3. A survey of possible higher oxides, which have been postulated as possible chlorine sinks in the stratosphere, was also carried out. The rate of formation of ClO dimer was measured as a function of temperature and pressure. Measurements were made of both the decay of ClO and the formation of the dimer. By comparing these rates it was determined that virtually all of the ClO was converted to the dimer under stratospheric conditions, and that the other ClO reactions were not important under these conditions.

Greene, Frank T.↗
NASA NTRS1995

Reduced dimer production in solar-simulator-pumped continuous wave iodine lasers based on model simulations and scaling and pumping studies

A numerical rate equation model for a continuous wave iodine laser with longitudinally flowing gaseous lasant is validated by approximating two experiments that compare the perfluoroalkyl iodine lasants n-C3F7I and t-C4F9I. The salient feature of the simulations is that the production rate of the dimer (C4F9)2 is reduced by one order of magnitude relative to the dimer (C3F7)2. The model is then used to investigate the kinetic effects of this reduced dimer production, especially how it improves output power. Related parametric and scaling studies are also presented. When dimer production is reduced, more monomer radicals (t-C4F9) are available to combine with iodine ions, thus enhancing depletion of the laser lower level and reducing buildup of the principal quencher, molecular iodine. Fewer iodine molecules result in fewer downward transitions from quenching and more transitions from stimulated emission of lasing photons. Enhanced depletion of the lower level reduces the absorption of lasing photons. The combined result is more lasing photons and proportionally increased output power.

Costen, Robert C.↗
NASA NTRS1998

Kinetic preference for the 3'-5'-linked dimer in the reaction of guanosine 5'-phosphorylmorpholinamide with deoxyguanosine 5'-phosphoryl-2-methylimidazolide as a function of poly(C) concentration

The formation of the internucleotide bond in diguanylate synthesis was studied in aqueous solution at pH 8 and 0.2 M Mg2+ in the presence and absence of polycytidylate, poly(C). The investigation was simplified by using guanosine 5'-phosphorylmorpholinamide, mor-pG, which can act only as a nucleophile, and deoxyguanosine 5'-phosphoryl-2-methylimidazolide, 2-MeImpdG, which can act only as an electrophile. The time-dependent product distribution was monitored by high-performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC/MS). In the absence of poly(C) the reaction between mor-pG and 2-MeImpdG yielded small amounts of the dimer mor-pGpdG with a regioselectivity of 2'-5':3'-5' = 3.5. In the presence of poly(C) dimer yields increased and a reversal in regioselectivity occurred; both effects were in proportion to the concentration of the polymer. The results can be quantitatively explained with the proposition that poly(C), acting as the template, catalyzes the reaction between template-bound monomers by about a factor of 4-5 over the reaction in solution and yields dimers with a regioselectivity of 2'-5':3'-5' approximately 0.33. These findings illustrate the intrinsic preference of guanosine monomers to correctly self-assemble on the appropriate template.

NASA Discipline Exobiology↗
NASA NTRS1989

Oligomerization of deoxynucleoside-bisphosphate dimers: template and linkage specificity

Evidence is presented that a poly(U) template selectively favors the oligomerization of the activated, 3'-5' pyrophosphate-linked dimer pdAppdAp, in comparison with the 3'-3' and 5'-5' linked dimers. In the absence of poly(U), the 5'-5' linked dimer is the most reactive, and chains are formed which are more than 60 monomer units in length.

NASA Discipline Exobiology↗
NASA NTRS1984

Self-deactivation of water vapor - Role of the dimer

A phenomenological multiple-relaxation theory of the deactivation rate constant for the nu-2 (1 - 0) bending mode of water vapor is presented which incorporates the role not only of the excited monomer but also of the bound molecular complex, in particular the dimer. The deactivation takes place by means of three parallel processes: (1) collisional deexcitation of the excited monomer, (2) a two-step reaction involving association and spontaneous redissociation of an H2O collision complex, and (3) spontaneous dissociation of the stably bound H2O dimer. Oxygen, but not nitrogen or argon, serves as an effective chaperon for the formation of the activated complex. This observation explains the impurity dependence of the self-deactivation rate constant of water vapor. Analysis of an ultrasonic absorption peak based on the third process yields values for the standard entropy and enthalpy of dissociation of the stably bound H2O dimer.

Zuckerwar, A. J.↗
NASA NTRS1988

Stability and photochemistry of ClO dimers formed at low temperature in the gas phase

The recent observations of elevated concentrations of the ClO radical in the austral spring over Antarctica have implicated catalytic destruction by chlorine in the large depletions seen in the total ozone column. One of the chemical theories consistent with an elevated concentration of the ClO is a cycle involving the formation of the ClO dimer through the association reaction: ClO + ClO = Cl2O2 and the photolysis of the dimer to give the active Cl species necessary for O3 depletion. Here, researchers report experimental studies designed to characterize the dimer of ClO formed by the association reaction at low temperatures. ClO was produced by static photolysis of several different precursor systems: Cl sub 2 + O sub 3; Cl sub 2 O sub 2; OClO + Cl sub 2 O spectroscopy in the U.V. region, which allowed the time dependence of Cl sub 2, Cl sub 2 O, ClO, OClO, O sub 3 and other absorbing molecules to be determined.

Cox, R. A.↗
NASA NTRS1990

Ultraviolet spectrum and chemical reactivity of the ClO dimer

The ClO dimer was prepared by photolysis (wavelength greater than 300 nm) of Cl2/Cl2O or Cl2/O3 mixtures or by photolysis of Cl2O alone. Temperatures were in the range 195-217 K, and experiments were carried out both in the gas phase and in the cryogenic solvents CF4, CO2, and N2O. Dimer cross sections in the range 190-400 nm are reported both in the gas phase and in the solvents. Results indicate that ClOOCl is the only dimer structure formed as a stable product. Upper limits of 1 x 10 to the -19th and 1 x 10 to the -20th cu cm/s are placed on the reactions of ClOOCl with O3 and with itself, respectively.

Demore, W. B.↗
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.↗
NASA NTRS1992

Ultraviolet Spectrum And Chemical Reactivity Of CIO Dimer

Report describes experimental study of ultraviolet spectrum and chemical reactivity of dimer of chlorine monoxide (CIO). Objectives are to measure absorption cross sections of dimer at near-ultraviolet wavelengths; determine whether asymmetrical isomer (CIOCIO) exists at temperatures relevant to Antarctic stratosphere; and test for certain chemical reactions of dimer. Important in photochemistry of Antarctic stratosphere.

Demore, William B.↗
NASA NTRS1992

Application of the Stogryn-Hirschfelder treatment of weak dimers to planetary atmospheres

The thermodynamics of carbon dioxide dimerization is treated as an example of the evaluation of weak dimer populations in planetary atmospheres (e.g., Mars and Venus). Two approaches considered are the Stogryn-Hirschfelder (1960) treatment using the Lennard-Jones interaction and calculations based on recent quantum chemical data. Several improvements of these treatments are developed. It is indicated that carbon dioxide dimers may be less or more abundant at the surfaces of Mars or Venus, respectively, than is suggested by previous calculations.

Slanina, Zdenek↗
NASA NTRS2000

Visualizing the Impurity Depletion Zone Around Holoferritin Crystals Growing in Gel with Ferritin Dimers

Colorless transparent apoferritin (Mr = 450KDa) crystals have been grown from gel with Cd(2+) as precipitant in the presence of reddish brown-colored ferritin dimers (Mr = 900KDa). In agreement with our previous measurements, showing preferential trapping of dimers (distribution coefficient K = 4), the apoferritin crystals become strongly colored while the gel solution around them became nearly colorless. The depth of the depletion with respect to the colored dimer impurity allowed us to visualize the impurity depletion zone. Depletion with respect to impurity as compared to the crystallizing protein is discussed.

Chernov, A. A.↗
NASA NTRS1978

Laser excited fluorescence in the cesium-xenon excimer and the cesium dimer

Argon ion laser lines are used to excite fluorescence in a mixture of cesium and xenon. Excimer band fluorescence is observed at higher pressures (about 1 atm) while at lower pressures (several torr) a diffuse fluorescence due to the cesium dimer is observed whose character changes with exciting wavelength. The excimer fluorescence is shown to be directly related to the location of the exciting wavelength within previously measured Cs/Xe line shapes. This fact suggests that the excimer systems may be efficiently pumped through these line shapes. Qualitative energy-level schemes are proposed to explain the observations in both the excimer and dimer systems.

Exton, R. J.↗
NASA NTRS1981

Electron-temperature dependence of dissociative recombination of electrons with N2/+/.N2 dimer ions

The variation with electron temperature of the dissociative recombination of electrons with N2(+).N2 dimer ions is investigated in light of the importance of such ions in the lower ionosphere and in laser plasmas. Dissociative recombination coefficients were determined by means of a microwave afterglow mass spectrometer technique for electron temperatures from 300-5600 K and an ion and neutral temperature of 300 K. The recombination coefficient is found to be proportional to the -0.41 power of the electron temperature in this range, similar to that observed for the CO(+).CO dimer ion and consistent with the expected energy dependence for a fast dissociative process.

Whitaker, M.↗
NASA NTRS1982

Theory of metal atom-water interactions and alkali halide dimers

Theoretical studies of the interactions of metal atoms with water and some of its isoelectronic analogs, and of the properties of alkali halides and their aggregates are discussed. Results are presented of ab initio calculations of the heats of reaction of the metal-water adducts and hydroxyhydrides of Li, Be, B, Na, Mg, and Al, and of the bond lengths and angles an; the heats of reaction for the insertion of Al into HF, H2O, NH3, H2S and CH3OH, and Be and Mg into H2O. Calculations of the electron affinities and dipole moments and polarizabilities of selected gas phase alkali halide monomers and dimers are discussed, with particular attention given to results of calculations of the polarizability of LiF taking into account electron correlation effects, and the polarizability of the dimer (LiF)2.

Jordan, K. D.↗