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All sourcesNASA NTRSDOE OSTI
NASA NTRS2012

Characterizing Abundances of Volatiles in Comets Through Multiwavelength Observations

Recently, there have been complimentary observations from multiple facilities to try to unravel the chemical complexity of comets. Incorporating results from various techniques, including: single-dish millimeter wavelength observations, interferometers, and/or IR spectroscopy, one can gain further insight into the abundances, production rates, distributions, and formation mechanisms of molecules in these objects [I]. Such studies have provided great detail towards molecules with a-typical chemistries, such as H2CO [2]. We report spectral observations of C/2007 N3 (Lulin), C/2009 R1 (McNaught), 103P/Hartley 2, and C/2009 P1 (Garradd) with the Arizona Radio Observatory's SMT and 12-m telescopes, as well as the NRAO Greenbank telescope and IRTF-CSHELL. Multiple parent volatiles (HCN, CH3OH, CO, CH4, C2H6, and H2O) as well as a number of daughter products (CS and OH) have been detected in these objects. We will present a comparison of molecular abundances in these comets to those observed in others, supporting a long-term effort of building a comet taxonomy based on composition. Previous work has revealed a range of abundances of parent species (from "organics-poor" to "organics-rich") with respect to water among comets [3,4,5], however the statistics are still poorly constrained and interpretations of the observed compositional diversity are uncertain. We gratefully acknowledge support from the NSF Astronomy and Astrophysics Program, the NASA Planetary Astronomy Program, NASA Planetary Atmospheres Program, and the NASA Astrobiology Program.

Milam, Stefanie N.↗
NASA NTRS1985

Mass loss from red giants - Infrared spectroscopy

A discussion is presented of IR spectroscopy, particularly high-resolution spectroscopy in the approximately 1-20 micron band, as it impacts the study of circumstellar envelopes. The molecular bands within this region contain an enormous amount of information, especially when observed with sufficient resolution to obtain kinematic information. In a single spectrum, it is possible to resolve lines from up to 50 different rotational/vibrational levels of a given molecule and to detect several different isotopic variants. When high resolution techniques are combined with mapping techniques and/or time sequence observations of variable stars, the resulting information can paint a very detailed picture of the mass-loss phenomenon. To date, near-IR observations have been made of 20 molecular species. CO is the most widely observed molecule and useful information has been gleaned from the observed rotational excitation, kinematics, time variability and spatial structure of its lines. Examples of different observing techniques are discussed in the following sections.

Wannier, P. G.↗
NASA NTRS2004

Miniaturized multiplex label-free electronic chip for rapid nucleic acid analysis based on carbon nanotube nanoelectrode arrays

BACKGROUND: Reducing cost and time is the major concern in clinical diagnostics, particularly in molecular diagnostics. Miniaturization technologies have been recognized as promising solutions to provide low-cost microchips for diagnostics. With the recent advancement in nanotechnologies, it is possible to further improve detection sensitivity and simplify sample preparation by incorporating nanoscale elements in diagnostics devices. A fusion of micro- and nanotechnologies with biology has great potential for the development of low-cost disposable chips for rapid molecular analysis that can be carried out with simple handheld devices. APPROACH: Vertically aligned multiwalled carbon nanotubes (MWNTs) are fabricated on predeposited microelectrode pads and encapsulated in SiO2 dielectrics with only the very end exposed at the surface to form an inlaid nanoelectrode array (NEA). The NEA is used to collect the electrochemical signal associated with the target molecules binding to the probe molecules, which are covalently attached to the end of the MWNTs. CONTENT: A 3 x 3 microelectrode array is presented to demonstrate the miniaturization and multiplexing capability. A randomly distributed MWNT NEA is fabricated on each microelectrode pad. Selective functionalization of the MWNT end with a specific oligonucleotide probe and passivation of the SiO2 surface with ethylene glycol moieties are discussed. Ru(bpy)2+ -mediator-amplified guanine oxidation is used to directly measure the electrochemical signal associated with target molecules. SUMMARY: The discussed MWNT NEAs have ultrahigh sensitivity in direct electrochemical detection of guanine bases in the nucleic acid target. Fewer than approximately 1000 target nucleic acid molecules can be measured with a single microelectrode pad of approximately 20 x 20 microm2, which approaches the detection limit of laser scanners in fluorescence-based DNA microarray techniques. MWNT NEAs can be easily integrated with microelectronic circuitry and microfluidics for development of a fully automated system for rapid molecular analysis with minimum cost.

Carbon↗
NASA NTRS1972

Molecular beams in chemistry.

The molecular-beam technique is a means for producing isolated atoms or molecules within a narrow range of speed and solid angle. The phenomena studied with molecular beams can be classified as single-particle interactions, many-particle interactions, and two particle-interactions. The results of scattering experiments fall into two categories including collisions that do not result in atomic rearrangements and collisions that do. Experimental methods are discussed, giving attention to low-energy beams, high-energy beams, and intermediate-energy beams. Examples are presented to illustrate the information that can be obtained from elastic, inelastic, and reactive scattering.

Jordan, J. E.↗
NASA NTRS1998

Tropospheric Wind Profile Measurements with a Direct Detection Doppler Lidar

Research has established the importance of global tropospheric wind measurements for large scale improvements in numerical weather prediction. In addition, global wind measurements provide data that are fundamental to the understanding and prediction of global climate change. These tasks are closely linked with the goals of the NASA Earth Science Enterprise and Global Climate Change programs. NASA Goddard has been actively involved in the development of direct detection Doppler lidar methods and technologies to meet the wind observing needs of the atmospheric science community. In this paper we describe a recently developed prototype wind lidar system using a direct detection Doppler technique for measuring wind profiles from the surface through the troposphere. This system uses a pulsed ND:YAG laser operating at 1064 nm as the transmitter. The laser pulse is directed to the atmosphere using a 40 cm diameter scan mirror. The portion of the laser energy backscattered from aerosols and molecules is collected by a 40 cm diameter telescope and coupled via fiber optics into the Doppler receiver. Single photon counting APD's are used to detect the atmospheric backscattered signal. The principle element of the receiver is a dual bandpass tunable Fabry Perot etalon which analyzes the Doppler shift of the incoming laser signal using the double edge technique. The double edge technique uses two high resolution optical filters having bandpasses offset relative to one another such that the 'edge' of the first filter's transmission function crosses that of the second at the half power point. The outgoing laser frequency is located approximately at the crossover point. Due to the opposite going slopes of the edges, a Doppler shift in the atmospheric backscattered laser frequency produces a positive change in signal for one filter and a negative change in the second filter. Taking the ratio of the two edge channel signals yields a result which is directly proportional to the component of the wind along the line-of-sight of the laser. Measuring the radial wind in several directions provides sufficient information to determine the true wind speed and direction. The lidar has operated from our laboratory at Goddard since June, 1997. Wind profiles have been obtained to altitudes of 12 km with a vertical resolution of 330 in. Vector wind data are obtained by rotating the scan mirror to measure line-of-sight wind profiles for at least two azimuth angles at an elevation angle of 45 degrees. The precision of the data as determined from the standard deviation of multiple independent lidar profiles is in the range of 1 to 3 m/sec up to 10 km. Good agreement is obtained when the lidar data are compared with the upper air rawinsonde soundings taken at Dulles airport. Examples of the wind lidar data will be presented along with a description of the instrument and future developments.

Gentry, Bruce M.↗
NASA NTRS1983

Simultaneous multiple-point velocity measurements using laser-induced iodine fluorescence

A technique is demonstrated for measuring velocity at multiple locations in a plane of a gaseous flowfield using Doppler-shifted absorption with fluorescence detection from iodine molecules, excited by a sheet of tunable single-axial-mode argon-ion laser radiation at 514.5 nm. Measurements were made simultaneously at 10,000 points in an iodine-seeded supersonic flow field with a 100 x 100 element photodiode array camera and were found to agree well with a numerical solution for the velocity field. The accuracy with which a component of velocity can be measured is limited, in the current approach, by the iodine linewidth to about 5 m/sec.

Mcdaniel, J. C.↗
NASA NTRS1989

Better PFAE's From Direct Fluorination

New low-molecular-weight perfluoroalkylethers (PFAE's) synthesized by direct fluorination in experimental study. Correlated viscosity and oxidation characteristics of PFAE's with structures to evaluate suitability as high-temperature lubricants and hydraulic fluids. Direct fluorination process attractive because it often involves single-step reaction and uses cheap starting materials. Versatile: produces highly branched ethers as well as polyethers containing more than two sequential carbon atoms in polymer chains. Such molecules cannot be made by conventional techniques.

Jones, W. R., Jr.↗
NASA NTRS1988

Diode laser harmonic spectroscopy applied to in situ measurements of atmospheric trace molecules

With the emergence of lead-salt diode laser technology, a broad and important IR spectral region, roughly 3-30 microns, became accessible to tunable laser spectroscopy. More recent advances in fabrication techniques have provided experimenters with relatively high power quasi-single-mode high-temperature lasers that are readily adapted to compact automated instruments for field experiments. An especially attractive capability of diode lasers is the ease of using them for simultaneous multiconstituent sampling in the atmosphere. This paper presents a summary description of field instruments for atmospheric research which employ diode lasers and second-harmonic detection. Representative results obtained with some of these instruments are presented.

Loewenstein, Max↗
NASA NTRS1980

On the low lying singlet states of BeO

Calculations of the ground and low-lying singlet states of BeO are performed in order to gain an understanding of the techniques needed to treat the excited states of other, more complex, ionic molecules. The MCSCF and CI calculations are based on a Gaussian basis set of slightly better than double zeta plus polarization quality for single configuration descriptions of the states. The calculated X-A and X-B state separations are found to be in agreement with experimental measurements. The 1 Sigma - and 1 Delta states are predicted to lie approximately 40,000 kaysers above the ground state and are identified as the C and D states.The 2 1 Pi state is found to be approximately 15,000 kaysers and the 3 1 Sigma + state is found to be approximately 65,000 kaysers above the ground state.

Bauschlicher, C. W., Jr.↗
NASA NTRS1985

Two-frequency laser-induced fluorescence technique for rapid velocity-field measurements in gas flows

A technique is presented for measurements of two-dimensional velocity fields in gas flows. The single-mode frequency of an argon-ion laser is fixed in the wing of an absorption line of iodine molecules that are seeded at low level in the flow of interest. The emitted fluorescence is detected with an image-intensified 100 x 100 photodiode-array camera. two pairs of counterpropagating laser sheets sequentially probe the flow to determine two velocity components. The frequency in one pair is shifted with respect to the other by an acousto-optic modulator. This two-frequency scheme eliminates the need to determine the slope of the line externally and offers the potential for combined pressure and velocity-field measurements.

Hiller, B.↗
NASA NTRS1998

New AFM Techniques for Investigating Molecular Growth Mechanisms of Protein Crystals

Atomic Force Microscopy (AFM) has emerged as a powerful technique for investigating protein crystal growth. Earlier AFM studies were among the first to demonstrate that these crystals grew by dislocation and 2D nucleation growth mechanisms [1]. These investigations were restricted to the micron range where only surface features, such as dislocation hillocks and 2D islands are visible. Most AFM instruments can scan at higher resolutions and have the potential to resolve individual protein molecules at nanometer ranges. Such scans are essential for determining the molecular packing arrangements on crystal faces and for probing the growth process at the molecular level. However, at this resolution the AFM tip influences the image produced, with the resulting image being a convolution of the tip shape and the surface morphology [2]. In most studies this problem is resolved by deconvoluting the image to obtain the true surface morphology. Although deconvolution routines work reasonably well for simple one- dimensional shapes, for complex surfaces this approach does not produce accurate results. In this study we devised a new approach which takes advantage of the precise molecular order of crystal surfaces, combined with the knowledge of individual molecular shapes from the crystallographic data of the protein and the AFM tip shape. This information is used to construct expected theoretical AFM images by convoluting the tip shape with the constructed crystal surface shape for a given surface packing arrangement. By comparing the images from actual AFM scans with the constructed ones for different possible surface packing arrangements, the correct packing arrangement can be conclusively determined. This approach was used in this study to determine the correct one from two possible packing arrangements on (I 10) faces of tetragonal lysozyme crystals. Another novel AFM technique was also devised to measure the dimension of individual growth units of the crystal faces. Measuring these units was not attempted before and most studies have assumed that the growth unit consisted of individual protein molecules. The linescan mode of AFM instruments allows the crystal surface to be scanned along a single line. By scanning across a growth step an image showing the motion of the step is obtained. Normally such an image shows a straight line for continuous and constant step velocity. In this study by increasing the scan rate and by decreasing the step velocity (by decreasing the supersaturation), we were able to capture images of individual growth events, shown by jump discontinuities in the step line. By suitable integration of the image the growth unit dimension in the scanned direction can be obtained. Since multiple units can be involved in the growth process it is necessary to collect a statistically relevant sample before drawing conclusions about the growth mechanism. This technique was successfully employed to obtain the dimensions of growth units for the (110) face, showing that they consisted of various aggregates corresponding to the 43 helices in the crystal structure.

Li, Huayu↗
NASA NTRS1986

Simultaneous measurements of velocity and pressure fields in subsonic and supersonic flows through image-intensified detection of laser-induced fluorescence

An optical technique is presented for combined, spatially resolved measurements of two-dimensional velocity and pressure fields in compressible flows. The single-mode frequency of an argon laser is fixed in the wing of an absorption line of iodine molecules, seeded in an underexpanded round jet of nitrogen gas. The emitted fluorescence, being proportional to the amount of absorbed radiation and hence the absorption line-shape function, is detected with an intensified 100 x 100 photodiode array camera. A single-microchannel-plate image intensifier is fiber-optically coupled to the array in order to improve time resolution and SNR. Three components of the velocity vector in a cross-sectional plane are sequentially probed with four laser sheets from three different directions. By shifting the laser frequency in one of the sheets with a piezo-tuned intra-cavity etalon, the slope of the absorption line can be measured in situ in order to provide the required scaling factor for the velocity measurement. With its short measurement times of less than 250 ms, this method is well suited for blow-down wind tunnel experiments.

Hiller, B.↗
NASA NTRS2004

Monte Carlo Technique Used to Model the Degradation of Internal Spacecraft Surfaces by Atomic Oxygen

Atomic oxygen is one of the predominant constituents of Earth's upper atmosphere. It is created by the photodissociation of molecular oxygen (O2) into single O atoms by ultraviolet radiation. It is chemically very reactive because a single O atom readily combines with another O atom or with other atoms or molecules that can form a stable oxide. The effects of atomic oxygen on the external surfaces of spacecraft in low Earth orbit can have dire consequences for spacecraft life, and this is a well-known and much studied problem. Much less information is known about the effects of atomic oxygen on the internal surfaces of spacecraft. This degradation can occur when openings in components of the spacecraft exterior exist that allow the entry of atomic oxygen into regions that may not have direct atomic oxygen attack but rather scattered attack. Openings can exist because of spacecraft venting, microwave cavities, and apertures for Earth viewing, Sun sensors, or star trackers. The effects of atomic oxygen erosion of polymers interior to an aperture on a spacecraft were simulated at the NASA Glenn Research Center by using Monte Carlo computational techniques. A two-dimensional model was used to provide quantitative indications of the attenuation of atomic oxygen flux as a function of the distance into a parallel-walled cavity. The model allows the atomic oxygen arrival direction, the Maxwell Boltzman temperature, and the ram energy to be varied along with the interaction parameters of the degree of recombination upon impact with polymer or nonreactive surfaces, the initial reaction probability, the reaction probability dependence upon energy and angle of attack, degree of specularity of scattering of reactive and nonreactive surfaces, and the degree of thermal accommodation upon impact with reactive and non-reactive surfaces to be varied to allow the model to produce atomic oxygen erosion geometries that replicate actual experimental results from space. The degree of erosion of various interior locations was compared with the erosion that would occur external to the spacecraft. Results of one cavity model indicate that, at depths into a two-dimensional cavity that are equal to 10 cavity widths, the erosion on the walls of the cavity is less than that on the top surface by over 2 orders of magnitude. Wall erosion near the surface of a cavity depends on which wall is receiving direct atomic oxygen attack. However, deep in the cavity little difference is present. Testing of various cavity models such as these gives spacecraft designers an indication of the level of threat to sensitive interior surfaces for different geometries. Even though the Monte Carlo model is two-dimensional, it can be used to provide qualitative information about spacecraft openings that are three-dimensional by offering reasonable insight as to the nature of the attenuation of damage that occurs within a spacecraft in low Earth orbit. As shown, there is more erosion on the side seeing direct atomic oxygen attack until a depth of approximately 5 times the width of the opening, where the erosion is the same on both sides.

Banks, Bruce A.↗
NASA NTRS2012

Compound-Specific Isotopic Analysis of Meteoritic Amino Acids as a Tool for Evaluating Potential Formation Pathways

Measurements of stable hydrogen, carbon, and nitrogen isotopic ratios (delta D, delta C-13, delta N-15) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may point towards the most likely of these proposed pathways. The technique of gas chromatography coupled with mass spectrometry and isotope ratio mass spectrometry provides compound-specific structural and isotopic information from a single splitless injection, enhancing the amount of information gained from small amounts of precious samples such as carbonaceous chondrites. We have applied this technique to measure the compound-specific C, N, and H isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites. We are using these measurements to evaluate predictions of expected isotopic enrichments from potential formation pathways and environments, leading to a better understanding of the origin of these compounds.

Elsila, Jamie E.↗
NASA NTRS1990

Simultaneous measurements of velocity, temperature, and pressure using rapid CW wavelength-modulation laser-induced fluorescence of OH

In high speed flows, laser induced fluorescence (LIF) on Doppler shifted transitions is an attractive technique for velocity measurement. LIF velocimetry was applied to combined single-point measurements of velocity, temperature, and pressure and 2-D imaging of velocity and pressure. Prior to recent research using NO, LIF velocimetry in combustion related flows relied largely on the use of seed molecules. Simultaneous, single-point LIF measurements is reported of velocity, temperature, and pressure using the naturally occurring combustion species OH. This experiment is an extension of earlier research in which a modified ring dye laser was used to make time resolved temperature measurements behind reflected shock waves by using OH absorption an in postflame gases by using OH LIF. A pair of fused-silica rhombs mounted on a single galvanonmeter in an intracavity-doubled Spectra-Physics 380 ring laser permit the UV output to be swept continuously over a few wave numbers at an effective frequency of 3kHz.

Chang, A. Y.↗
NASA NTRSDate not supplied

Demonstration of Frequency-Scanning Burst-mode Filtered Rayleigh Scattering for Multi-Parameter Gas-Phase Measurements

Filtered Rayleigh scattering (FRS) is a diagnostic technique used for measurements of macroscopic properties of a gas. The FRS signal is passed through a narrow bandwidth molecular filter, commonly gaseous iodine, to measure the broadening and Doppler-shift of the scattering light from the molecules of the gas flow. However, in single-frequency, intensity-based approaches, the effects of pressure, temperature, and velocity can be difficult to deconvolve. To overcome this challenge, frequency-scanning FRS has been used to quasi-spectrally resolve the signal. In this work, a frequency-scanned, burst-mode laser was used to perform scanning FRS in an underexpanded jet to measure temperature, pressure, and radial velocity at measurement rates up to 1 kHz which is ~100,000 times faster than prior implementations of scanning FRS.

filtered Rayleigh scattering↗
NASA NTRS1972

Preferential orientation of CO adsorption on Ni as determined by extended Hueckel calculations.

The adsorption of CO on the nickel surface has been calculated using a modified extended Hueckel technique for a number of different orientations of the CO with respect to the nickel surface. The calculations show that double site adsorption with the CO molecule normal to the surface and the carbon atom closest to the metal gives the most stable configuration (2.57 eV). The single site absorbs with an energy of 2.39 eV. However, other configurations also give fairly large bonding energies. The CO normal to the surface with oxygen closest to the metal gives a heat of adsorption of 0.37 eV. Two-center adsorption with the CO axis parallel to the surface and the molecule symmetrically placed between the nearest neighbors gives a chemisorption energy of 1.34 eV. These values compare with an experimental value of 1.98 eV.

Robertson, J. C.↗
NASA NTRS1990

New parameter-free polarization potentials in low-energy positron collisions

The polarization potential plays a decisive role in shaping up the cross sections in low energy positron collisions with atoms and molecules. However, its inclusion without involving any adjustable parameter, is still a challenge. Various other techniques employed so far for positron collisions are summarized, and a new, nonadjustable and very simple form of the polarization potential for positron-atom (molecule) collisions below the threshold of positronium formation is discussed. This new recently proposed potential is based on the correlation energy of a single positron in a homogeneous electron gas. The correlation energy was calculated by solving the Schrodinger equation of the positron-electron system and fitted to an analytical form in various ranges of the density parameter. In the outside region, the correlation energy is joined smoothly with the correct asymptotic form. This new positron correlation polarization (PCOP) potential was tested on several atomic and molecular targets such as the Ar, CO, and CH4. The results on the total and differential cross sections on these targets are shown along with the experimental data where available.

Jain, Ashok↗