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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

Application of Ni-63 photo and corona discharge ionization for the analysis of chemical warfare agents and toxic wastes

Over the past decade, advances in instrumental design and refinements in the understanding of ion molecule reactions at atmospheric pressure enabled the application of Ion Mobility Spectrometry (IMS) as a simple inexpensive and sensitive analytical method for the detection of organic trace compounds. Positive and negative gas-phase ions for ion mobility spectrometry have been produced by a variety of methods, including photo-ionization, laser multi photon ionization, surface ionization, corona discharge ionization. The most common ion source used in ion mobility spectrometry is a radioactive Ni-63 foil which is favored due to simplicity, stability, convenience, and high selectivity. If reactant ions like (H2O(n)H)(+) or (H2O(n)O2)(-) dominate in the reaction region, nearly all kinds of compounds with a given proton or electron affinity; are ionized. However, the radioactivity of the Ni-63 foil is one disadvantage of this ion source that stimulates the development and application of other ionization techniques. In this paper, we report analyses of old chemical warfare agents and toxic wastes using Bruker RAID ion mobility spectrometers. Due to the modular construction of the measuring cell, the spectrometers can be equipped with different ion sources. The combined use of Ni-63, photo- and corona discharge ionization allows the identification of different classes of chemical compounds and yields in most cases comparable results.

Stach, J.↗
NASA NTRS1993

Carbonaceous chondrite clasts in the howardites Bholghati and EET87513

Twenty-two carbonaceous chondrite clasts from the two howardites Bholghati and EET87513 were analyzed. Clast N from EET87513 is a fragment classified as CM2 material on the basis of texture, bulk composition, mineralogy, and bulk O isotopic composition. Carbonaceous chondrite clasts from Bholghati, for which less data are available because of their small size, can be divided into two petrologic types: C1 and C2. C1 clasts are composed of opaque matrix with rare coarse-grained silicates as individual mineral fragments; textures resemble CI meteorites and some dark inclusions from CR meteorites. Opaque matrix is predominantly composed of flaky saponite; unlike typical CI and CR meteorites, serpentine is absent in the samples we analyzed. C2 clasts contain chondrules, aggregates, and individual fragments of coarse-grained silicates in an opaque matrix principally composed of saponite and anhydrous ferromagnesian silicates with flaky textures similar to phyllosilicates. These anhydrous ferromagnesian silicates are interpreted as the product of heating of pre-existing serpentine. The carbonaceous chondrite clasts we have studied from these two howardites are, with one notable exception (clast N from EET87513), mineralogically distinct from typical carbonaceous chondrites. However, these clasts have very close affinities to carbonaceous chondrites and have also experienced thermal metamorphism and aqueous alteration, but to different degrees.

Buchanan, P. C.↗
NASA NTRS1994

A discharge flow-photoionization mass spectrometric study of the FO(X 2 Pi i) radical. Photoionization efficiency spectrum and ionization energy

Photoionization efficiency spectra of FO were measured over the wavelength range 80.0-100.0 nm and in the ionization threshold region, 94.0-100.0 nm, using a discharge flow-photoionization mass spectrometer apparatus coupled to a synchrotron radiation source. FO was generated by the reaction of F2P atoms with NO3 and via a F2O2 discharge. A value of 12.78 +/- 0.03 eV was obtained for the adiabatic ionization energy of FO from photoion thresholds which corresponds to FO(+)(X 3 Sigma -) from FO(X 2 Pi i). These results, which are the first to be obtained by direct Photo-ionization mass spectrometry (PIMS) measurements, corroborate those of a photoelectron spectroscopy (PES) study; however, the ionization energy determined here is free from interferences due to other species which complicated the PES measurement. A value of 109.5 +/- 8.0 kJ/mol for Delta f H 0 298(FO) is computed from the present value of IE(FO) and a previous appearance energy measurement, and a value for the proton affinity of FO is calculated to be 511.5 +/- 10.0 kJ/mol.

Zhang, Zhengyu↗
NASA NTRS1995

Advanced compilation techniques in the PARADIGM compiler for distributed-memory multicomputers

The PARADIGM compiler project provides an automated means to parallelize programs, written in a serial programming model, for efficient execution on distributed-memory multicomputers. .A previous implementation of the compiler based on the PTD representation allowed symbolic array sizes, affine loop bounds and array subscripts, and variable number of processors, provided that arrays were single or multi-dimensionally block distributed. The techniques presented here extend the compiler to also accept multidimensional cyclic and block-cyclic distributions within a uniform symbolic framework. These extensions demand more sophisticated symbolic manipulation capabilities. A novel aspect of our approach is to meet this demand by interfacing PARADIGM with a powerful off-the-shelf symbolic package, Mathematica. This paper describes some of the Mathematica routines that performs various transformations, shows how they are invoked and used by the compiler to overcome the new challenges, and presents experimental results for code involving cyclic and block-cyclic arrays as evidence of the feasibility of the approach.

Su, Ernesto↗
NASA NTRS1996

Robust Stabilization of a Class of passive Nonlinear Systems

The problem of feedback stabilization is considered for a class of nonlinear, finite dimensional, time invariant passive systems that are affine in control. Using extensions of the Kalman-Yakubovch lemma, it is shown that such systems can be stabilized by a class of finite demensional, linear, time-invariant controllers which are strictly positive real in the weak or marginal sense. The stability holds regardless of model uncertainties, and is therefore, robust.

Joshi, Suresh M.↗
NASA NTRS1994

A Redetermination of the Dissociation Energy of MgO(+)

In 1986, we reported a dissociation energy (D(sub 0) of 2.31 eV for the X(sup 2)Pi ground state of MgO(+). This value was determined by computing the dissociation energy to the Mg(2+) + O(-) limit and adjusting the value to the Mg(+) + O limit using the experimental Ionization Potential (IP) of Mg(+) and the Electron Affinity (EA) of O. The success of this method relies on the assumption that there is little covalent contribution to the bonding. The very small (0.04 eV) correlation contribution to the binding energy was taken as corroboration for the validity of this approach. Our earlier theoretical value was estimated to be accurate to at least 0.2 eV. It is in excellent agreement with the subsequent value of 2.30 +/- 0.13 eV determined by Freiser and co-workers from photodissociation experiments. It is also consistent with the upper (less than 3.1 eV) and lower (greater than 1.1 eV) bounds determined by Rowe obtained by studying the reactions of Mg(+) with 03 and NO2. However, it is inconsistent with an upper bound of 1.7 eV reported by Kappes and Staley based on their failure to observe MgO(+) in the reaction of Mg(+) with N2O. The picture became somewhat clouded, however, by the recent guided-ion beam mass spectrometric studies of Dalleska and Armentrout. Their initial analysis of the reaction data for Mg(+) + O2 lead to a bond dissociation energy of 2.92 +/- 0.25 eV, which is considerably larger than the value of 2.47 +/- 0.06 eV deduced from their studies of the Mg(+)+NO2 reaction.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1997

Moessbauer Mineralogy on the Moon: The Lunar Regolith

A first-order requirement for spacecraft missions that land on solid planetary objects is instrumentation for mineralogical analyses. For purposes of providing diagnostic information about naturally-occurring materials, the element iron is particularly important because it is abundant and multivalent. Knowledge of the oxidation state of iron and its distribution among iron-bearing mineralogies tightly constrains the types of materials present and provides information about formation and modification (weathering) processes. Because Moessbauer spectroscopy is sensitive to both the valence of iron and its local chemical environment, the technique is unique in providing information about both the relative abundance of iron-bearing phases and oxidation state of the iron. The Moessbauer mineralogy of lunar regolith samples (primarily soils from the Apollo 16 and 17 missions to the Moon) were measured in the laboratory to demonstrate the strength of the technique for in situ mineralogical exploration of the Moon. The regolith samples were modeled as mixtures of five iron-bearing phases: olivine, pyroxene, glass, ilmenite, and metal. Based on differences in relative proportions of iron associated with these phases, volcanic ash regolith can be distinguished from impact-derived regolith, impact-derived soils of different geologic affinity (e.g., highlands, maria) can be distinguished on the basis of their constituent minerals, and soil maturity can be estimated. The total resonant absorption area of the Moessbauer spectrum can be used to estimate total FeO concentrations.

Morris, Richard V.↗
NASA NTRS1997

Temperature-Dependent Kinetics Studies of the Reactions Br((sup 2)P3/2) + H2S yields SH + HBr and Br((sup 2)P3/2) + CH3SH yields CH3S + HBr. Heats of Formation of SH and CH3S Radicals

Time resolved resonance fluorescence detection of Br(sup 2)P3/2) atom disappearance or appearance following 266-nm laser flash photolysis of CF2Br2/H2S/H2/N2, CF2Br2/CH3SH/H2/N2, Cl2CO/H2S/HBr/N2, and CH3SSCH3/HBr/H2/N2 mixtures has been employed to study the kinetics of the reactions Br((sup 2)P3/2) + H2S = SH + HBr (1,-1) and Br((sup2)P3/2) + CH3SH = CH3S + HBr (2, -2) as a function of temperature over the range 273-431K. Arrhenius expressions in units of 10(exp -12) cu cm/molecule/s which describe the results are k1 = (14.2 +/- 3.4) exp[(-2752 +/- 90)/T],(k-1) = (4.40 +/- 0.92) exp[(-971 +/- 73)/T],k(2) = (9.24 +/- 1.15) exp[(-386 +/- 41)/T], and k(-2) = (1.46 +/-0.21) exp[(-399 +/-41)/T; errors are 2 sigma and represent precision only. By examining Br((sup 2)P3/2) equilibrium kinetics following 355nm laser flash photolysis of Br2/CH3SH/H2/N2 mixtures, a 298 K rate coefficient of (1.7 +/- 0.5) x 10(exp -10) cu cm/molecule/s has been obtained for the reaction CH3S + Br2 yields CH3SBr + Br. To our knowledge, these are the first kinetic data reported for each of the reactions studied. Measured rate coefficients, along with known rate coefficients for similar radical + H2S, CH3SH, HBr,Br2 reactions are considered in terms of possible correlations of reactivity with reaction thermochemistry and with IP - EA, the difference between the ionization potential of the electron donor and the electron affinity of the electron acceptor. Both thermochemical and charge-transfer effects appear to be important in controlling observed reactivities. Second and third law analyses of the equilibrium data for reactions 1 and 2 have been employed to obtain the following enthalpies of reaction in units of kcal/mol: for reaction 1, Delta-H(298) = 3.64 +/- 0.43 and Delta-H(0) = 3.26 +/-0.45; for reaction 2, Delta-H(298) = -0.14 +/- 0.28 and Delta-H(0) = -0.65 +/- 0.36. Combining the above enthalpies of reaction with the well-known heats of formation of Br, HBr, H2S, and CH3SH gives the following heats of formation for the RS radicals in units of kcal/mol: Delta-H(sub f)(sub 0)(SH) = 34.07 +/- 0.72, Delta-H(sub f)(sub 298)(SH) = 34.18 +/- 0.68, Delta-H(sub f)(sub 0)(CH3S) = 31.44 +/- 0.54, Delta-H(sub f)(sub 298)(CH3S) = 29.78 +/- 0.44; errors are 2 sigma and represent estimates of absolute accuracy. The SH heat of formation determined from our data agrees well with literature values but has reduced error limits compared to other available values. The CH3S heat of formation determined from our date is near the low end of the range of previous estimates and is 3-4 kcal/mol lower than values derived from recent molecular beam photofragmentation studies.

Nicovich, J. M.↗
NASA NTRS1997

A Comparison of PETSC Library and HPF Implementations of an Archetypal PDE Computation

Two paradigms for distributed-memory parallel computation that free the application programmer from the details of message passing are compared for an archetypal structured scientific computation a nonlinear, structured-grid partial differential equation boundary value problem using the same algorithm on the same hardware. Both paradigms, parallel libraries represented by Argonne's PETSC, and parallel languages represented by the Portland Group's HPF, are found to be easy to use for this problem class, and both are reasonably effective in exploiting concurrency after a short learning curve. The level of involvement required by the application programmer under either paradigm includes specification of the data partitioning (corresponding to a geometrically simple decomposition of the domain of the PDE). Programming in SPAM style for the PETSC library requires writing the routines that discretize the PDE and its Jacobian, managing subdomain-to-processor mappings (affine global- to-local index mappings), and interfacing to library solver routines. Programming for HPF requires a complete sequential implementation of the same algorithm, introducing concurrency through subdomain blocking (an effort similar to the index mapping), and modest experimentation with rewriting loops to elucidate to the compiler the latent concurrency. Correctness and scalability are cross-validated on up to 32 nodes of an IBM SP2.

Hayder, M. Ehtesham↗
NASA NTRS1997

Efficient algorithms for robust feature matching

One of the basic building blocks in any point-based registration scheme involves matching feature points that are extracted from the sensed image to their counterparts in the reference image. This leads to the fundamental problem of point matching: given two sets of points, find the affine transformation that transforms one point set so that its distance from the other point set is minimized. Because of measurement errors and the presence of outlying data points, it is important that the distance measure between two point sets be robust to these effects. We measure distances using the generalized Hausdorff distance. Point matching can be a computationally intensive task, and there have been a number of algorithms and approaches proposed for solving this problem both theoretical and applied. We present two approaches to the point matching problem, in an attempt to reduce the computational complexity of the problem, while still providing guarantees on the quality of the final match. Our first method is an approximation algorithm, which is loosely based on a branch-and-bound approach due to Huttenlocher and Rucklidge. We show that by varying the approximation error bounds, it is possible to achieve a tradeoff between the quality of the match and the running time of the algorithm. Our second method involves a Monte Carlo method for accelerating the search process used in the first algorithm. With high probability this method succeeds in finding an approximately optimal match. We establish the efficiency of our approaches empirically.

Mount, David M.↗
NASA NTRS1999

Characterization of Human Bone Alkaline Phosphatase in Pichia Pastoris

A soluble form of human bone alkaline phosphatase has been expressed in a recombinant strain of the methylotrophic yeast Pichia pastoris. We constructed a plasmid containing cDNA encoding for human bone alkaline phosphatase, with the hydrophobic carboxyl terminal portion deleted. Alkaline phosphatase was secreted into the medium to a level of 32mg/L when cultured in shake flasks, and enzyme activity was 12U/mg, as measured by a spectrophotometric assay. By conversion to a fermentation system, a yield of 880mg/L has been achieved with an enzyme activity of 968U/mg. By gel electrophoresis analysis, it appears that greater than 50% of the total protein in the fermentation media is alkaline phosphatase. Although purification procedures are not yet completely optimized, they are expected to include filtration, ion exchange and affinity chromatography. Our presentation will focus on the purification and crystallization results up to the time of the conference. Structural data should provide additional information on the role of alkaline phosphatase in normal bone mineralization and in certain bone mineralization anomalies.

Malone, Christine C.↗
NASA NTRS1998

Structure of Pseudoknot PK26 Shows 3D Domain Swapping in an RNA

3D domain swapping provides a facile pathway for the evolution of oligomeric proteins and allosteric mechanisms and a means for using monomer-oligomer equilibria to regulate biological activity. The term "3D domain swapping" describes the exchange of identical domains between two protein monomers to create an oligomer. 3D domain swapping has, so far, only been recognized in proteins. In this study, the structure of the pseudoknot PK26 is reported and it is a clear example of 3D domain swapping in RNA. PK26 was chosen for study because RNA pseudoknots are required structures in several biological processes and they arise frequently in in vitro selection experiments directed against protein targets. PK26 specifically inhibits HIV-1 reverse transcriptase with nanomolar affinity. We have now determined the 3.1 A resolution crystal structure of PK26 and find that it forms a 3D domain swapped dimer. PK26 shows extensive base pairing between and within strands. Formation of the dimer requires the linker region between the pseudoknot folds to adopt a unique conformation that allows a base within a helical stem to skip one base in the stacking register. Rearrangement of the linker would permit a monomeric pseudoknot to form. This structure shows how RNA can use 3D domain swapping to build large scale oligomers like the putative hexamer in the packaging RNA of bacteriophage Phi29.

Lietzke, Susan E↗
NASA NTRS1999

Secondary Electron Emission Spectroscopy of Diamond Surfaces

This report presents the results of the secondary electron emission spectroscopy study of hydrogenated diamond surfaces for single crystals and chemical vapor-deposited polycrystalline films. One-electron calculations of Auger spectra of diamond surfaces having various hydrogen coverages are presented, the major features of the experimental spectra are explained, and a theoretical model for Auger spectra of hydrogenated diamond surfaces is proposed. An energy shift and a change in the line shape of the carbon core-valence-valence (KVV) Auger spectra were observed for diamond surfaces after exposure to an electron beam or by annealing at temperatures higher than 950 C. This change is related to the redistribution of the valence-band local density of states caused by hydrogen desorption from the surface. A strong negative electron affinity (NEA) effect, which appeared as a large, narrow peak in the low-energy portion of the spectrum of the secondary electron energy distribution, was also observed on the diamond surfaces. A fine structure in this peak, which was found for the first time, reflected the energy structure of the bottom of the conduction band. Further, the breakup of the bulk excitons at the surface during secondary electron emission was attributed to one of the features of this structure. The study demonstrated that the NEA type depends on the extent of hydrogen coverage of the diamond surface, changing from the true type for the completely hydrogenated surface to the effective type for the partially hydrogenated surface.

Krainsky, Isay L.↗
NASA NTRS1998

Tests of the Giant Impact Hypothesis

The giant impact hypothesis has gained popularity as a means of explaining a volatile-depleted Moon that still has a chemical affinity to the Earth. As Taylor's Axiom decrees, the best models of lunar origin are testable, but this is difficult with the giant impact model. The energy associated with the impact would be sufficient to totally melt and partially vaporize the Earth. And this means that there should he no geological vestige of Barber times. Accordingly, it is important to devise tests that may be used to evaluate the giant impact hypothesis. Three such tests are discussed here. None of these is supportive of the giant impact model, but neither do they disprove it.

Jones, J. H.↗
NASA NTRS2000

Robust Control of Uncertain Systems via Dissipative LQG-Type Controllers

Optimal controller design is addressed for a class of linear, time-invariant systems which are dissipative with respect to a quadratic power function. The system matrices are assumed to be affine functions of uncertain parameters confined to a convex polytopic region in the parameter space. For such systems, a method is developed for designing a controller which is dissipative with respect to a given power function, and is simultaneously optimal in the linear-quadratic-Gaussian (LQG) sense. The resulting controller provides robust stability as well as optimal performance. Three important special cases, namely, passive, norm-bounded, and sector-bounded controllers, which are also LQG-optimal, are presented. The results give new methods for robust controller design in the presence of parametric uncertainties.

Joshi, Suresh M.↗
NASA NTRS1999

Automatic Data Distribution for CFD Applications on Structured Grids

Data distribution is an important step in implementation of any parallel algorithm. The data distribution determines data traffic, utilization of the interconnection network and affects the overall code efficiency. In recent years a number data distribution methods have been developed and used in real programs for improving data traffic. We use some of the methods for translating data dependence and affinity relations into data distribution directives. We describe an automatic data alignment and placement tool (ADAPT) which implements these methods and show it results for some CFD codes (NPB and ARC3D). Algorithms for program analysis and derivation of data distribution implemented in ADAPT are efficient three pass algorithms. Most algorithms have linear complexity with the exception of some graph algorithms having complexity O(n(sup 4)) in the worst case.

Frumkin, Michael↗
NASA NTRS2000

Automatic Data Distribution for CFD Applications on Structured Grids

Data distribution is an important step in implementation of any parallel algorithm. The data distribution determines data traffic, utilization of the interconnection network and affects the overall code efficiency. In recent years a number data distribution methods have been developed and used in real programs for improving data traffic. We use some of the methods for translating data dependence and affinity relations into data distribution directives. We describe an automatic data alignment and placement tool (ADAFT) which implements these methods and show it results for some CFD codes (NPB and ARC3D). Algorithms for program analysis and derivation of data distribution implemented in ADAFT are efficient three pass algorithms. Most algorithms have linear complexity with the exception of some graph algorithms having complexity O(n(sup 4)) in the worst case.

Frumkin, Michael↗