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At least 487 records · Page 27

The Measurement of Sulfur Oxidation Products and Their Role in Homogeneous Nucleation

An improved version of a transverse ion source was developed which uses selected ion chemical ionization mass spectrometry techniques inside of a particle nucleation flow tube. These new techniques are very unique, in that the chemical ionization is done inside of the flow tube rather than by having to remove the compounds and clusters of interest which are lost on first contact,with any surfaces. The transverse source is also unique because it allows the ion reaction time to be varied over more than an order of magnitude, which in turn makes possible the separation of ion induced cluster growth from the charging of preexisting molecular clusters. As a result of combining these unique capabilities, the first ever measurements of prenucleation molecular clusters were performed. These clusters are the intermediate stage of growth in the gas-to-particle conversion process. This new technique provides a means of observing clusters containing 2, 3, 4, ... and up to about 8 sulfuric acid molecules, where the critical cluster size under these measurement conditions was about 4 or 5. Thus, the nucleation process can now be directly observed and even growth beyond the critical cluster size can be investigated. The details of this investigation are discussed in a recently submitted paper, which is included as Appendix A. Measurements of the diffusion coefficient of sulfuric acid and sulfuric acid clustered with a water molecule have also been performed. The measurements are also discussed in more detail in another recently submitted paper which is included as Appendix B. The empirical results discussed in both of these papers provide a critical test of present nucleation theories. They also provide new hope for resolving many of the huge discrepancies between field observation and model prediction of particle nucleation. The second part of the research conducted under this project was directed towards the development of new chemical ionization techniques for measuring sulfur oxidation products.

Eisele, F. L.↗

Studies of the role of metastables and doubly ionized species in the chemical and thermal structure of the Venusian and Martian ionospheres

Models of the upper atmospheres of Mars and Venus were constructed using Viking and Pioneer Venus data. The neutral densities, with the exception of NO, N(4S), N(2D) and N(2P) were taken from the measured values, along with the neutral, ion, and electron temperatures. Using solar fluxes and relevant cross sections, the production rates of ions and neutral fragments by photo and electron impact processes were computed. These production rates were combined with chemical production rates and loss along with one dimensional transport eddy diffusion, molecular and ambi polar diffusion, and thermal diffusion, to determine the densities of ions and odd nitrogen species. Preliminary calculations show that the chemistry of metastables and doubly ionized species is important in the ionospheres of Mars and Venus. Production of N(+) in metastable reactions is particularly important, and it explains the discrepancy between the measurements of earlier models. Production of CO(+) is also affected. Reactions of O(++) and O(+)(2D) with N2 have important consequences for the escape rate of atomic nitrogen from the Martian atmosphere.

Fox, J. L.↗

Novel Molecular Architectures Developed for Improved Solid Polymer Electrolytes for Lithium Polymer Batteries

Lithium-based polymer batteries for aerospace applications need the ability to operate in temperatures ranging from -70 to 70 C. Current state-of-the-art solid polymer electrolytes (based on amorphous polyethylene oxide, PEO) have acceptable ionic conductivities (10-4 to 10-3 S/cm) only above 60 C. Higher conductivity can be achieved in the current systems by adding solvent or plasticizers to the solid polymer to improve ion transport. However, this can compromise the dimensional and thermal stability of the electrolyte, as well as compatibility with electrode materials. One of NASA Glenn Research Center's objectives in the PERS program is to develop new electrolytes having unique molecular architectures and/or novel ion transport mechanisms, leading to good ionic conductivity at room temperature and below without solvents or plasticizers.

Meador, Mary Ann B.↗

A technique for mass spectrometer measurements of atomic and molecular oxygen in the lower thermosphere

A neutral mass spectrometer with a quasi-open ion source was flown on each of the Atmosphere Explorer (AE) C, D, and E satellites. The three instruments provided an opportunity to study the effects of different source insert materials on the source surface chemistry. It was found that, after a period of conditioning in space, the recombination coefficient of atomic oxygen on gold appears to be substantially lower than it is on Nichrome V. The lower recombination coefficient on gold allows the spectrometer to directly measure a significant fraction of the incident atomic oxygen, making it possible to distinguish between ambient O and O2. Equations are developed to calculate the atomic and molecular oxygen densities. Preliminary measurements of molecular oxygen densities obtained by this technique agree well with measurements taken in the fly-through mode of operation.

Kayser, D. C.↗

Secondary ion mass spectrometry study of ex situ annealing of epitaxial GaAs grown on Si substrates

Samples of epitaxial GaAs grown on (100) Si substrates using molecular beam epitaxy were annealed at four different temperatures, from 800 to 950 C. Following annealing, the samples were analyzed using secondary ion mass spectrometry. Depth profiles of Ga, As, and Si reveal optimum conditions for annealing, and place a lower limit on a damage threshold for GaAs/Si substrates.

Radhakrishnan, G.↗

Time scales for molecule formation by ion-molecule reactions

Analytical solutions are obtained for nonlinear differential equations governing the time-dependence of molecular abundances in interstellar clouds. Three gas-phase reaction schemes are considered separately for the regions where each dominates. The particular case of CO, and closely related members of the Oh and CH families of molecules, is studied for given values of temperature, density, and the radiation field. Nonlinear effects and couplings with particular ions are found to be important. The time scales for CO formation range from 100,000 to a few million years, depending on the chemistry and regime. The time required for essentially complete conversion of C(+) to CO in the region where the H3(+) chemistry dominates is several million years. Because this time is longer than or comparable to dynamical time scales for dense interstellar clouds, steady-state abundances may not be observed in such clouds.

Langer, W. D.↗

Progress in Predicting Ionic Cocrystal Formation: The Case of Ammonium Nitrate

In contrast to the mature predictive frameworks applied to neutral cocrystals, ionic cocrystals, those including an ion pair, are difficult to design. Furthermore, they are generally excluded categorically from studies which correlate specific molecular properties to cocrystal formation, leaving the prospective ionic cocrystal engineer with few clear avenues to success. Herein ammonium nitrate, an energetic oxidizing salt, is targeted for cocrystallization in a potential coformer group selected based on likely interactions with the nitrate ion as revealed in the Cambridge Structural Database; six novel ionic cocrystals were discovered. Molecular descriptors previously identified as being related to neutral cocrystal formation were examined across the screening group but showed no relationship with ionic cocrystal formation. High packing coefficient is shown to be a constant among the successful coformers in the set and is utilized to directly target two more successful coformers, bypassing the need for a large screening group.

Andrew J. Bennett↗

The spectroscopy of comets: Introductory remarks

Emphasis in cometary spectroscopy is on production rates, becuase they open the door to more fundamental clues about the origin and the history of the solar system, through the understanding of comet chemistry. In order to establish production rates quantitatively, suggestion are provided, in particular: to study the lifetimes of all hypothetical parents, against all processes of decay, namely photodissociations, photoionizations and ion-molecule reactions; and to study the velocity of all molecular fragments resulting from all the decay processes, through the balance sheet of the energy distribution before and after each decay process.

Delsemme, A. H.↗

Chemical evolution of primitive solar system bodies

Observations on organic molecules and compounds containing biogenic elements in the interstellar medium and in the primitive bodies of the solar system are reviewed. The discovery of phosphorus molecular species in dense interstellar clouds, the existence of organic ions in the dust and gas phase of the comas of Comet Halley, and the presence of presolar, deuterium-hydrogen ratios in the amino acids of carbonaceous chondrites are discussed. The relationships between comets, dark asteroids, and carbonaceous chondrites are examined. Also, consideration is given to the chemical evolution of Titan, the primitive earth, and early Mars.

Oro, J.↗

A novel beta-glucosidase from the cell wall of maize (Zea mays L.): rapid purification and partial characterization

Plants have a variety of glycosidic conjugates of hormones, defense compounds, and other molecules that are hydrolyzed by beta-glucosidases (beta-D-glucoside glucohydrolases, E.C. 3.2.1.21). Workers have reported several beta-glucosidases from maize (Zea mays L.; Poaceae), but have localized them mostly by indirect means. We have purified and partly characterized a 58-Ku beta-glucosidase from maize, which we conclude from a partial sequence analysis, from kinetic data, and from its localization is not identical to any of those already reported. A monoclonal antibody, mWP 19, binds this enzyme, and localizes it in the cell walls of maize coleoptiles. An earlier report showed that mWP19 inhibits peroxidase activity in crude cell wall extracts and can immunoprecipitate peroxidase activity from these extracts, yet purified preparations of the 58 Ku protein had little or no peroxidase activity. The level of sequence similarity between beta-glucosidases and peroxidases makes it unlikely that these enzymes share epitopes in common. Contrary to a previous conclusion, these results suggest that the enzyme recognized by mWP19 is not a peroxidase, but there is a wall peroxidase closely associated with the 58 Ku beta-glucosidase in crude preparations. Other workers also have co-purified distinct proteins with beta-glucosidases. We found no significant charge in the level of immunodetectable beta-glucosidase in mesocotyls or coleoptiles that precedes the red light-induced changes in the growth rate of these tissues.

Non-NASA Center↗

The ferredoxin-thioredoxin system of a green alga, Chlamydomonas reinhardtii: identification and characterization of thioredoxins and ferredoxin-thioredoxin reductase components

The components of the ferredoxin-thioredoxin (FT) system of Chlamydomonas reinhardtii have been purified and characterized. The system resembled that of higher plants in consisting of a ferredoxin-thioredoxin reductase (FTR) and two types of thioredoxin, a single f and two m species, m1 and m2. The Chlamydomonas m and f thioredoxins were antigenically similar to their higher-plant counterparts, but not to one another. The m thioredoxins were recognized by antibodies to both higher plant m and bacterial thioredoxins, whereas the thioredoxin f was not. Chlamydomonas thioredoxin f reacted, although weakly, with the antibody to spinach thioredoxin f. The algal thioredoxin f differed from thioredoxins studied previously in behaving as a basic protein on ion-exchange columns. Purification revealed that the algal thioredoxins had molecular masses (Mrs) typical of thioredoxins from other sources, m1 and m2 being 10700 and f 11500. Chlamydomonas FTR had two dissimilar subunits, a feature common to all FTRs studied thus far. One, the 13-kDa ("similar") subunit, resembled its counterpart from other sources in both size and antigenicity. The other, 10-kDa ("variable") subunit was not recognized by antibodies to any FTR tested. When combined with spinach, (Spinacia oleracea L.) thylakoid membranes, the components of the FT system functioned in the light activation of the standard target enzymes from chloroplasts, corn (Zea mays L.) NADP-malate dehydrogenase (EC 1.1.1.82) and spinach fructose 1,6-bisphosphatase (EC 3.1.3.11) as well as the chloroplast-type fructose 1,6-bisphosphatase from Chlamydomonas. Activity was greatest if ferredoxin and other components of the FT system were from Chlamydomonas. The capacity of the Chlamydomonas FT system to activate autologous FBPase indicates that light regulates the photosynthetic carbon metabolism of green algae as in other oxygenic photosynthetic organisms.

NASA Discipline Exobiology↗

Production of Solar Cells in Space from Non Specific Ores by Utilization of Electronically Enhanced Sputtering

An ideal method of construction in space would utilize some form of the Universal Differentiator and Universal Constructor as described by Von Neumann (1). The Universal Differentiator is an idealized non ore specific extractive device which is capable of breaking any ore into its constituent elements, and the Universal Constructor can utilize these elements to build any device with controllability to the nanometer scale. During the Human Exploration Initiative program in the early 1990s a conceptual study was done (2) to understand whether such devices were feasible with near term technology for the utilization of space resources and energy. A candidate system was proposed which would utilize electronically enhanced sputtering as the differentiator. Highly ionized ions would be accelerated to a kinetic energy at which the interaction between them and the lattice elections in the ore would be at a maximum. Experiments have shown that the maximum disintegration of raw material occurs at an ion kinetic energy of about 5 MeV, regardless of the composition and structure of the raw material. Devices that could produce charged ion beams in this energy range in space were being tested in the early 1990s. At this energy, for example an ion in a beam of fluorine ions yields about 8 uranium ions from uranium fluoride, 1,400 hydrogen and oxygen atoms from ice, or 7,000 atoms from sulfur dioxide ice. The ions from the disintegrated ore would then be driven by an electrical field into a discriminator in the form of a mass spectrometer, where the magnetic field would divert the ions into collectors for future use or used directly in molecular beam construction techniques. The process would require 10-7 Torr vacuum which would be available in space or on the moon. If the process were used to make thin film silicon solar cells (ignoring any energy inefficiency for beam production), then energy break even for solar cells in space would occur after 14 days.

Curreri, Peter A.↗

Measurement of Anomalously Strong Emission from the 1s-9p Transition in the Spectrum of H-like Phosphorus Following Charge Exchange with Molecular Hydrogen

We have measured K-shell x-ray spectra of highly ionized argon and phosphorus following charge exchange with molecular hydrogen at low collision energy in an electron beam ion trap using an x-ray calorimeter array with approx.6 eV resolution. We find that the emission at the high-end of the Lyman series is greater by a factor of two for phosphorus than for argon, even though the measurement was performed concurrently and the atomic numbers are similar. This does not agree with current theoretical models and deviates from the trend observed in previous measurements.

Leutenegger, M. A.↗

Calculation of the Frequency Distribution of the Energy Deposition in DNA Volumes by Heavy Ions

Radiation quality effects are largely determined by energy deposition in small volumes of characteristic sizes less than 10 nm representative of short-segments of DNA, the DNA nucleosome, or molecules initiating oxidative stress in the nucleus, mitochondria, or extra-cellular matrix. On this scale, qualitatively distinct types of molecular damage are possible for high linear energy transfer (LET) radiation such as heavy ions compared to low LET radiation. Unique types of DNA lesions or oxidative damages are the likely outcome of the energy deposition. The frequency distribution for energy imparted to 1-20 nm targets per unit dose or particle fluence is a useful descriptor and can be evaluated as a function of impact parameter from an ions track. In this work, the simulation of 1-Gy irradiation of a cubic volume of 5 micron by: 1) 450 (1)H(+) ions, 300 MeV; 2) 10 (12)C(6+) ions, 290 MeV/amu and 3) (56)Fe(26+) ions, 1000 MeV/amu was done with the Monte-Carlo simulation code RITRACKS. Cylindrical targets are generated in the irradiated volume, with random orientation. The frequency distribution curves of the energy deposited in the targets is obtained. For small targets (i.e. <25 nm size), the probability of an ion to hit a target is very small; therefore a large number of tracks and targets as well as a large number of histories are necessary to obtain statistically significant results. This simulation is very time-consuming and is difficult to perform by using the original version of RITRACKS. Consequently, the code RITRACKS was adapted to use multiple CPU on a workstation or on a computer cluster. To validate the simulation results, similar calculations were performed using targets with fixed position and orientation, for which experimental data are available [5]. Since the probability of single- and double-strand breaks in DNA as function of energy deposited is well know, the results that were obtained can be used to estimate the yield of DSB, and can be extended to include other targeted or non-target effects.

Plante, Ianik↗

Equation of state and phase diagram of dense hydrogen

The equation of state of hydrogen was calculated for specific volumes ranging from 0.01 to 0.0001 cm3/mole and for temperatures ranging from 200 to 1 million K. Three phases are considered: the molecular solid, the metallic solid and the fluid. Chemical equilibrium between molecules, atoms, ions and electrons is considered in calculating the properties of the fluid phase. Transitions between the three phases will be discussed. The triple point, where the three phases coexist, is calculated to occur at 2.3 Mbar and 1679 K. At higher temperatures and pressures, the molecular solid is unstable.

Kerley, G. I.↗