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Mass spectrometry.

Review of the current state of mass spectrometry, indicating its unique importance for advanced scientific research. Mass spectrometry applications in computer techniques, gas chromatography, ion cyclotron resonance, molecular fragmentation and ionization, and isotope labeling are covered. Details are given on mass spectrometry applications in bio-organic chemistry and biomedical research. As the subjects of these applications are indicated alkaloids, carbohydrates, lipids, terpenes, quinones, nucleic acid components, peptides, antibiotics, and human and animal metabolisms. Particular attention is given to the mass spectra of organo-inorganic compounds, inorganic mass spectrometry, surface phenomena such as secondary ion and electron emission, and elemental and isotope analysis. Further topics include mass spectrometry in organic geochemistry, applications in geochronology and cosmochemistry, and organic mass spectrometry.

Burlingame, A. L.↗

Investigation of ultraviolet fluxes of normal and peculiar stars

Data from Project Celescope, a program that photographed the ultraviolet sky, in order to study several problems in current astrophysics are analyzed. Two star clusters, the Pleiades and the Hyades, reveal differences between the two that we are unable to explain simply from their differences in chemical abundance, rotation, or reddening. Data for Orion show large scatter, which appears to be in the sense that the Orion stars are too faint for their ground-based photometry. Similarly, many supergiants in the association Sco OB1 are too faint in the ultraviolet, but the ultraviolet brightness appears to be only poorly correlated with spectral type. Ultraviolet Celescope data for several groups of peculiar stars have also been analyzed. The strong He I stars are too faint in the ultraviolet, possibly owing to enhancement of O II continuous opacity due to oxygen overabundance. The Be stars appear to have ultraviolet colors normal for their MK spectral types. The P Cygni stars are considerably fainter than main-sequence stars of comparable spectral type, probably owing, at least in part, to line blocking by resonance lines of multiply ionized light metals. The Wolf-Rayet stars have ultraviolet color temperatures of O stars.

Deutschman, W. A.↗

The nature of the bonding in the transition metal trimers

The electronic structure of the transition metal (TM) trimers was studied by comparing the bonding in the Ca3, Sc3, and Cu3 molecules. The complete active space SCF/externally contracted configuration interaction (CI) ratio for the low-lying states of Sc3 and Sc3(+) and the SCF/CI ratio for Ca3 and Cu3 trimers, all for near equilateral triangle geometries, were calculated. In addition, vertical excitation energies for Cu3 were computed, leading to a new assignment of the upper state in the resonant two-photon ionization spectrum. Based on these studies, bonding in other TM trimers was discussed.

Walch, Stephen P.↗

The ultraviolet spectrum of Beta Lyrae

The high-resolution UV spectrum of Beta Lyrae observed with the IUE satellite between 1980 and 1986 is analyzed. A complete list of line identifications for the entire spectral range of the IUE (1225-3125 A) is presented. The main spectral features are P Cygni profiles of resonance lines of high ionization states typical of stellar winds, some of which are combined with a broad emission feature due probably to an accretion disk; P Cygni profiles due to moderately ionized atoms in the iron group (mostly Fe III and Ni III); and absorption lines of elements in lower ionization stages, such as S II, Si II (higher multiplets), Ni II, and a large number of Fe II lines.

Mazzali, Paolo A.↗

Structure of 2,4-Diaminopyrimidine - Theobromine Alternate Base Pairs

We report the structure of clusters of 2,4-diaminopyrimidine with 3,7-dimethylxanthine (theobromine) in the gas phase determined by IR-UV double resonance spectroscopy in both the near-IR and mid-IR regions in combination with ab initio computations. These clusters represent potential alternate nucleobase pairs, geometrically equivalent to guanine-cytosine. We have found the four lowest energy structures, which include the Watson-Crick base pairing motif. This Watson-Crick structure has not been observed by resonant two-photon ionization (R2PI) in the gas phase for the canonical DNA base pairs.

Gengeliczki, Zsolt↗

Barium release system

A chemical system is described for releasing a good yield of free barium neutral atoms and barium ions in the upper atmosphere and interplanetary space for the study of the geophysical properties of the medium. The barium is released in the vapor phase so that it can be ionized by solar radiation and also be excited to emit resonance radiation in the visible range. The ionized luminous cloud of barium becomes a visible indication of magnetic and electrical characteristics in space and allows determination of these properties over relatively large areas at a given time.

Lewis, B. W.↗

Total photoionization cross sections of atomic oxygen from threshold to 44.3A

The relative cross section of atomic oxygen for the production of singly charged ions has been remeasured in more detail and extended to cover the wavelength range 44.3 to 910.5 A by the use of synchrotron radiation. In addition, the contribution of multiple ionization to the cross sections has been measured allowing total photoionization cross sections to be obtained below 250 A. The results have been made absolute by normalization to previously measured data. The use of synchrotron radiation has enabled measurements of the continuum cross section to be made between the numerous autoionizing resonances that occur near the ionization thresholds. This in turn has allowed a more critical comparison of the various theoretical estimates of the cross section to be made. The series of autoionizing resonances leading to the 4-P state of the oxygen ion have been observed for the first time in an ionization type experiment and their positions compared with both theory and previous photographic recordings.

Angel, G. C.↗

Precision tunable resonant microwave cavity

A tunable microwave cavity containing ionizable metallic vapor or gases and an apparatus for precisely positioning a microwave coupling tip in the cavity and for precisely adjusting at least one dimension of the cavity are disclosed. With this combined structure, resonance may be achieved with various types of ionizable gases. A coaxial probe extends into a microwave cavity through a tube. One end of the tube is retained in a spherical joint attached in the cavity wall. This allows the coaxial probe to be pivotally rotated. The coaxial probe is slideable within the tube thus allowing the probe to be extended toward or retracted from the center of the cavity.

Nakanishi, Shigeo↗

Accurate Cross Sections for Excitation of Resonance Transitions in Atomic Oxygen

Electron collision excitation cross sections for the resonance 2p(sup)4 (sup 3)P-2p(sup 3)3s (sup 3)S(sup 0), 2p(sup 4) (sup 3)P-2p(sup 3)3d (sup 3)D(sup 0), 2p4 (sup 3)P-2p(sup 3)3s (sup 3)D(sup 0), 2p(sup 4) (sup 3)P-2p(sup 3)3s (sup 3)P(sup 0) and 2p(sup 4) (sup 3)P-2s2p(sup 5) (sup 3)P(sup 0) transitions have been calculated by using the R matrix with a pseudostates approach for incident electron energies from near threshold to 100 eV. The excitation of these transition sgives rise to strong atomic oxygen emission features at 1304, 1027, 989, 878, and 792 Angstrom in the spectra of several planetary atmospheres. We included 22 spectroscopic bound and autoionizing states and 30 pseudostates in the close-coupling expansion. The target wave functions are chosen to properly account for the important correlation and relaxation effects. The effect of coupling to the continuum is included through the use of pseudostates. The contribution of the ionization continuum is significant for resonance transitions. Measured absolute direct excitation cross sections of 0 I are reported by experimental groups from the Jet Propulsion Laboratory and Johns Hopkins University. Good agreement is noted for the 2p(sup)4 (sup 3)P-2p(sup 3)3s (sup 3)S(sup 0) transition (lambda 1304 Ang) with measured cross sections from both groups that agree well with each other. There is disagreement between experiments for other transitions. Our results support the measured cross sections from the Johns Hopkins University for the 2p(sup 4) (sup 3)P-2p(sup 3)3d (sup 3)D(sup 0) and 2p4 (sup 3)P-2p(sup 3)3s (sup 3)D(sup 0) transitions, while for the 2p4 (sup 3)P-2p(sup 3)3s (sup 3)D(sup 0) transition the agreement is switched to the measured cross sections from the Jet Propulsion Laboratory.

Tayal, S. S.↗

Instrumentation Working Group Summary

The Instrumentation Working Group compiled a summary of measurement techniques applicable to gas turbine engine aerosol precursors and particulates. An assessment was made of the limits, accuracy, applicability, and technology readiness of the various techniques. Despite advances made in emissions characterization of aircraft engines, uncertainties still exist in the mechanisms by which aerosols and particulates are produced in the near-field engine exhaust. To adequately assess current understanding of the formation of sulfuric acid aerosols in the exhaust plumes of gas turbine engines, measurements are required to determine the degree and importance of sulfur oxidation in the turbine and at the engine exit. Ideally, concentrations of all sulfur species would be acquired, with emphasis on SO2 and SO3. Numerous options exist for extractive and non-extractive measurement of SO2 at the engine exit, most of which are well developed. SO2 measurements should be performed first to place an upper bound on the percentage of SO2 oxidation. If extractive and non-extractive techniques indicate that a large amount of the fuel sulfur is not detected as SO2, then efforts are needed to improve techniques for SO3 measurements. Additional work will be required to account for the fuel sulfur in the engine exhaust. Chemical Ionization Mass Spectrometry (CI-MS) measurements need to be pursued, although a careful assessment needs to be made of the sampling line impact on the extracted sample composition. Efforts should also be placed on implementing non-intrusive techniques and extending their capabilities by maximizing exhaust coverage for line-of-sight measurements, as well as development of 2-D techniques, where feasible. Recommendations were made to continue engine exit and combustor measurements of particulates. Particulate measurements should include particle size distribution, mass fraction, hydration properties, and volatile fraction. However, methods to ensure that unaltered samples are obtained need to be developed. Particulate speciation was also assigned a high priority for quantifying the fractions of carbon soot, PAH, refractory materials, metals, sulfates, and nitrates. High priority was also placed on performing a comparison of particle sizing instruments. Concern was expressed by the workshop attendees who routinely make particulate measurements about the variation in number density measured during in-flight tests by different instruments. In some cases, measurements performed by different groups of researchers during the same flight tests showed an order of magnitude variation. Second priority was assigned to measuring concentrations of odd hydrogen and oxidizing species. Since OH, HO2, H2O2, and O are extremely reactive, non-extractive measurements are recommended. A combination of absorption and fluorescence is anticipated to be effective for OH measurements in the combustor and at the engine exit. Extractive measurements of HO2 have been made in the stratosphere, where the ambient level of OH is relatively low. Use of techniques that convert HO2 to OH for combustor and engine exit measurements needs to be evaluated, since the ratio of HO2/OH may be 1% or less at both the combustor and engine exit. CI-MS might be a viable option for H2O2, subject to sampling line conversion issues. However, H2O2 is a low priority oxidizing species in the combustor and at the engine exit. Two candidates for atomic oxygen measurements are Resonance Enhanced Multi-Photon Ionization (REMPI) and Laser-Induced Fluorescence (LIF). Particulate measurement by simultaneous extractive and non-extractive techniques was given equal priority to the oxidizer measurements. Concern was expressed over the ability of typical ground test sampling lines to deliver an unaltered sample to a remotely located instrument. It was suggested that the sampling probe and line losses be checked out by attempting measurements using an optical or non-extractive technique immediately upstream of the sampling probe. This is a possible application for Laser Induced Incandescence (LII) as a check on the volume fraction of soot. Optical measurements of size distribution are not well developed for ultrafine particles less than about 20 nm in diameter, so a non-extractive technique for particulate size distribution cannot be recommended without further development. Carbon dioxide measurements need to be made to complement other extractive measurement techniques. CO2 measurements enable conversion of other species concentrations to emission indices. Carbon monoxide, which acts as a sink for oxidizing species, should be measured using non-extractive techniques. CO can be rapidly converted to CO2 in extractive probes, and a comparison between extractive and non-extractive measurements should be performed. Development of non-extractive techniques would help to assess the degree of CO conversion, and might be needed to improve the concentration measurement accuracy. Measurements of NO(x) will continue to be critical due to the role of NO and NO2 in atmospheric chemistry, and their influence on atmospheric ozone. Time-resolved measurements of temperature, velocity, and species concentrations were included on the list of desired measurement. Thermocouples are typically adequate for engine exit measurements. PIV and LDV are well established for obtaining velocity profiles. The techniques are listed in the accompanying table; are divided into extractive and non-extractive techniques. Efforts were made to include a measurement uncertainty for each technique. An assessment of the technology readiness was included.

Zaller, Michelle↗

Physics of magnetospheric boundary layers

This final report was concerned with the ideas that: (1) magnetospheric boundary layers link disparate regions of the magnetosphere-solar wind system together; and (2) global behavior of the magnetosphere can be understood only by understanding its internal linking mechanisms and those with the solar wind. The research project involved simultaneous research on the global-, meso-, and micro-scale physics of the magnetosphere and its boundary layers, which included the bow shock, the magnetosheath, the plasma sheet boundary layer, and the ionosphere. Analytic, numerical, and simulation projects were performed on these subjects, as well as comparisons of theoretical results with observational data. Other related activity included in the research included: (1) prediction of geomagnetic activity; (2) global MHD (magnetohydrodynamic) simulations; (3) Alfven resonance heating; and (4) Critical Ionization Velocity (CIV) effect. In the appendixes are list of personnel involved, list of papers published; and reprints or photocopies of papers produced for this report.

Cairns, Iver H.↗

Interstellar medium continuum, autoionization, and line absorption in the extreme ultraviolet

We provide a new estimate of the effective absorption cross section of the interstellar medium at extreme ultraviolet wavelengths. The cross section for neutral helium is discussed in detail. Two spectral features of interstellar neutral helium, the 504 A ionization edge and the autoionization resonance feature at 206 A, are detectable with existing instrumentation. Measurements of the autoionization feature in continuum sources will provide a direct estimate of the intervening neutral helium column; in many cases this will be the only method to obtain this parameter. Although continuum metal opacities are negligible at wavelengths greater than 50 A we find that metal line features should be detectable in continuum sources with high signal to noise observations. A selection of some of the most prominent lines expected is provided.

Rumph, Todd↗

Wind Variability of B Supergiants: The Rapid Rotator HD 64760 (B0.5 Ib) - No. 1

We present the results of a 6 day time series of observations of the rapidly rotating B0.5 Ib star HD 64760. We point out several reasons why such intermediate luminosity B supergiants are ideal targets for wind variability studies and then present our results that show the following: continuous wind activity throughout the 6 day run with the wind never in steady state for more than a few hr; wind variability very near nu = 0 km sec(exp -1) in the resonance lines from the lower ionization stages (Al III and C II); a distinct correlation between variability in the Si III ; lambda(lambda)1300 triplets, the strong C III (lambda)1247 singlet, and the onset of extremely strong wind activity, suggesting a connection between photospheric and wind activity; long temporal coherence in the behavior of the strong absorption events; evidence for large-scale spatial coherence, implied by a whole scale, simultaneous weakening in the wind absorption over a wide range in velocities; and ionization variability in the wind accompanying the largest changes in the absorption strengths of the wind lines. In addition, modeling of the wind lines provides the following information about the state the wind in HD 64760. The number of structures on the portion of a constant velocity surface occulting the stellar disk at a particular time must be quite small, while the number on the entire constant velocity surface throughout the wind must be large. The escape probability at low velocity is overestimated by a normal beta approx. 1 velocity law, perhaps due to the presence of low-velocity shocks deep in the wind or a shallow velocity gradient at low velocity. Estimates of the ionization structure in the wind indicate that the ionization ratios are not those expected from thermal equilibrium wind models or from an extrapolation of previous O star results. The large observed q(N V)/q(Si IV) ratio is almost certainly due to distributed X-rays, but the level of ionization predicted by distributed X-ray wind models is inconsistent with the predicted mass-loss rate. Thus, it is impossible to reconcile the observed ionization ratios and the predicted mass-loss rate within the framework of the available models.

Massa, Derck↗

The Nature of the Torus in the Heavily Obscured AGN Markarian 3: an X-Ray Study

In this paper, we report the results of an X-ray monitoring campaign on the heavily obscured Seyfert galaxy, Markarian 3, carried out between the fall of 2014 and the spring of 2015 with NuSTAR, Suzaku and XMMNewton. The hard X-ray spectrum of Markarian 3 is variable on all the time-scales probed by our campaign, down to a few days. The observed continuum variability is due to an intrinsically variable primary continuum seen in transmission through a large, but still Compton-thin column density (N(sub H) approx. 0.8-1.1 x 10(exp 24)/sq cm). If arranged in a spherical-toroidal geometry, the Compton scattering matter has an opening angle approx. 66deg, and is seen at a grazing angle through its upper rim (inclination angle approx. 70deg). We report a possible occultation event during the 2014 campaign. If the torus is constituted by a system of clouds sharing the same column density, this event allows us to constrain their number (17 +/- 5) and individual column density, [approx. (4.9 +/- 1.5) x 10(exp 22)/ sq cm]. The comparison of IR and X-ray spectroscopic results with state-of-the art torus models suggests that at least two-thirds of the X-ray obscuring gas volume might be located within the dust sublimation radius. We report also the discovery of an ionized absorber, characterized by variable resonant absorption lines due to He- and H-like iron. This discovery lends support to the idea that moderate column density absorbers could be due to clouds evaporated at the outer surface of the torus, possibly accelerated by the radiation pressure due to the central AGN emission leaking through the patchy absorber.

X-rays: individual: Markarian 3↗

High resolution X-ray spectroscopy of active galactic nuclei

After a brief review of the principal problems of AGN research, selected potential high-resolution observations are discussed with a view toward assessing their scientific value and the degree of resolution they will require. Two classes of observations pertaining directly to AGNs are discussed. Fe K-alpha spectroscopy relevant to the dynamical and thermal character of the emission line zones; and measurement of resonance line absorption by highly-ionized species in BL Lac objects, which should provide information about entrainment of interstellar material by relativistic jets. A third class of potentially important observations uses AGNs as background light sources in order to directly measure the distance to clusters of galaxies.

Krolik, Julian H.↗

NASA Tech Briefs, August 2009

Topics covered include: Aligning a Receiving Antenna Array to Reduce Interference; Collecting Ground Samples for Balloon-Borne Instruments; Tethered Pyrotechnic Apparatus for Acquiring a Ground Sample; Enhanced Video-Oculography System; Joint Carrier-Phase Synchronization and LDPC Decoding; Dual-Polarization, Sideband-Separating, Balanced Receiver for 1.5 THz Modular Battery Charge Controller; Efficient Multiplexer FPGA Block Structures Based on G4FETs; VLSI Microsystem for Rapid Bioinformatic Pattern Recognition; Low-Noise Amplifier for 100 to 180 GHz; Improved Fabrication of Ceramic Matrix Composite/Foam Core Integrated Structures; Inert Welding/Brazing Gas Filters and Dryers; Fabricating Copper Nanotubes by Electrodeposition; Reducing Aerodynamic Drag on Empty Open Cargo Vehicles; Rotary Percussive Auto-Gopher for Deep Drilling and Sampling; More About Reconfigurable Exploratory Robotic Vehicles; Thermostatic Valves Containing Silicone-Oil Actuators; Improving Heat Flux Performance of Flat Surface in Spray-Cooling Systems; Treating Fibrous Insulation to Reduce Thermal Conductivity; Silica-Aerogel Composites Opacified with La(sub0.7)Sr(sub0.3)MnO3; Cyclic Oxidation Behavior of CuCrAl Cold-Sprayed Coatings for Reusable Launch Vehicles; Ceramic Fiber Structures for Cryogenic Load-Bearing Applications; Elastomer Reinforced with Carbon Nanotubes; Biologically Inspired Purification and Dispersion of SWCNTs; A Technique for Adjusting Eigenfrequencies of WGM Resonators; Low-Pressure, Field-Ionizing Mass Spectrometer; Modifying Operating Cycles to Increase Stability in a LITS; Chamber for Simulating Martian and Terrestrial Environments; Algorithm for Detecting a Bright Spot in an Image; Extreme Programming: Maestro Style; Adaptive Behavior for Mobile Robots; Protocol for Communication Networking for Formation Flying; Planning Complex Sequences Using Compressed Representations; and Self-Supervised Learning of Terrain Traversability from Proprioceptive Sensors.

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