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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
NASA NTRS1982

Electronic levels and charge distribution near the interface of nickel

The energy levels in clusters of nickel atoms were investigated by means of a series of cluster calculations using both the multiple scattering and computational techniques (designated SSO) which avoids the muffin-tin approximation. The point group symmetry of the cluster has significant effect on the energy of levels nominally not occupied. This influences the electron transfer process during chemisorption. The SSO technique permits the approaching atom or molecule plus a small number of nickel atoms to be treated as a cluster. Specifically, molecular levels become more negative in the O atom, as well as in a CO molecule, as the metal atoms are approached. Thus, electron transfer from the nickel and bond formation is facilitated. This result is of importance in understanding chemisorption and catalytic processes.

Waber, J. T.↗
NASA NTRS2000

JavaGenes: Evolving Graphs with Crossover

Genetic algorithms usually use string or tree representations. We have developed a novel crossover operator for a directed and undirected graph representation, and used this operator to evolve molecules and circuits. Unlike strings or trees, a single point in the representation cannot divide every possible graph into two parts, because graphs may contain cycles. Thus, the crossover operator is non-trivial. A steady-state, tournament selection genetic algorithm code (JavaGenes) was written to implement and test the graph crossover operator. All runs were executed by cycle-scavagging on networked workstations using the Condor batch processing system. The JavaGenes code has evolved pharmaceutical drug molecules and simple digital circuits. Results to date suggest that JavaGenes can evolve moderate sized drug molecules and very small circuits in reasonable time. The algorithm has greater difficulty with somewhat larger circuits, suggesting that directed graphs (circuits) are more difficult to evolve than undirected graphs (molecules), although necessary differences in the crossover operator may also explain the results. In principle, JavaGenes should be able to evolve other graph-representable systems, such as transportation networks, metabolic pathways, and computer networks. However, large graphs evolve significantly slower than smaller graphs, presumably because the space-of-all-graphs explodes combinatorially with graph size. Since the representation strongly affects genetic algorithm performance, adding graphs to the evolutionary programmer's bag-of-tricks should be beneficial. Also, since graph evolution operates directly on the phenotype, the genotype-phenotype translation step, common in genetic algorithm work, is eliminated.

Globus, Al↗
NASA NTRS2006

Water Vapor Sensors Go Sky-High to Assure Aircraft Safety

JPL used a special tunable diode laser, which NASA scientists could tune to different wavelengths, like a radio being tuned to different frequencies, to accurately target specific molecules and detect small traces of gas. This tunable diode laser was designed to emit near-infrared light at wavelengths absorbed by the gas or gases being detected. The light energy being absorbed by the target gas is related to the molecules present. This is usually measured in parts per million or parts per billion. Multiple measurements are made every second, making the system quick to respond to variations in the target gas. NASA scientists developed this technology as part of the 1999 Mars Polar Lander mission to explore the possibility of life-giving elements on Mars. NASA has since used the tunable diode laser-based gas sensor on aircraft and on balloons to successfully study weather and climate, global warming, emissions from aircraft, and numerous other areas where chemical gas analysis is needed. SpectraSensors, Inc., was formed in 1999 as a spinoff company of JPL, to commercialize tunable diode laser-based analyzers for industrial gas-sensing applications (Spinoff 2000). Now, the San Dimas, California-based firm has come back to the market with a new product featuring the NASA-developed instrument for atmospheric monitoring. This instrument is now helping aircraft avoid hazardous weather conditions and enabling the National Weather Service to provide more accurate weather forecasts.

Source record↗
NASA NTRS1996

Determination of Highly Accurate Heats of Formation

Two approaches for directly computing a molecular heat of formation based on sophisticated ab initio electronic structure theory axe discussed and example calculations are presented for several molecules of interest in atmospheric chemistry including HNO and CICN. The accuracy of these approaches for a small subset of the molecules is demonstrated by comparison to very accurate experimental data. A third approach for evaluating accurate heats of formation consists of combining experimental and theoretical data. The potential for this method to provide reliable thermochemical data on many molecules using accurate experimental beats of formation for only a small number of species is demonstrated by giving accurate (Delta)H(sup 0, sub f) quantities for a host of fluorine, chlorine, and bromine oxide and nitrogen oxide compounds. Potential pitfalls in all three approaches are discussed.

Lee, Timothy J.↗
NASA NTRS1983

Thermal cis-trans isomerization of cis,cis-3,7-decadiene - A model for cis-1,4-polybutadiene

The thermal cis-trans isomerization of cis,cis-3,7-decadiene (DD), a model compound for cis-PBD, is reported. It is demonstrated that the rather low E for the polyalkenamer isomerizations compared with that for the 2-olefins is not an artifact of the solid polymer structures, but rather is characteristic of both small and large molecules possessing pairs of nonconjugated vinylene double bonds in a suitable arrangement.

Golub, M. A.↗
NASA NTRS1990

Definition study for temperature control in advanced protein crystal growth

Some of the technical requirements for an expedient application of temperature control to advanced protein crystal growth activities are defined. Lysozome was used to study the effects of temperature ramping and temperature gradients for nucleation/dissolution and consecutive growth of sizable crystals and, to determine a prototype temperature program. The solubility study was conducted using equine serum albumin (ESA) which is an extremely stable, clinically important protein due to its capability to bind and transport many different small ions and molecules.

Nyce, Thomas A.↗
NASA NTRS2002

Tetragonal Lysozyme Nucleation and Crystal Growth: The Role of the Solution Phase

Lysozyme, and most particularly the tetragonal form of the protein, has become the default standard protein for use in macromolecule crystal nucleation and growth studies. There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests this proteins crystal nucleation and growth is by addition of associated species that are preformed by standard reversible concentration-driven self association processes in the bulk solution. The evidence includes high resolution AFM studies of the surface packing and of growth unit size at incorporation, fluorescence resonance energy transfer measurements of intermolecular distances in dilute solution, dialysis kinetics, and modeling of the growth rate data. We have developed a selfassociation model for the proteins crystal nucleation and growth. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. Further, it indicates that nucleation and crystal growth are not distinct mechanistically, but identical, with the primary difference being the probability that the particle will continue to grow or dissolve. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small (M.W. = 14,400), a structured octamer in the 4(sub 3) helix configuration (the proposed average sized growth unit) would have a M.W. = 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm commonly attach to the crystal. These measurements were made at approximately saturation conditions, and they reflect the sizes of species that both added or desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it will be oriented to some degree in a flowing boundary layer, even at the low flow velocities measured about macromolecule crystals. Flow-driven effects resulting in misorientation upon addition to and incorporation into the crystal need only be a small fraction of a percentage to significantly affect the resulting crystal. One Earth, concentration gradient driven flow will maintain a high interfacial concentration, i.e., a high level (essentially that of the bulk solution) of solute association at the interface and higher growth rate. Higher growth rates mean an increased probability that misaligned growth units are trapped by subsequent growth layers before they can be desorbed and try again, or that the desorbing species will be smaller than the adsorbing species. In microgravity the extended diffusive boundary layer will lower the interfacial concentration. This results in a net dissociation of aggregated species that diffuse in from the bulk solution, i.e., smaller associated species, which are more likely able to make multiple attempts to correctly bind, yielding higher quality crystals.

Pusey, Marc L.↗
NASA NTRS2003

An Alternative Hypothesis for How Microgravity Improves Macromolecular Crystal Quality

There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests that for many proteins crystal nucleation and growth is by addition of associated species that are preformed by reversible concentration-driven self association processes in the bulk solution. We have developed a self-association model for the crystal nucleation and growth of the protein chicken egg lysozyme. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small an octamer in the 43 helix configuration (the proposed average sized growth unit) would have a M.W. approx. 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm (a 24-mer) commonly attach to the crystal. AFM results from Weichmann et al. (Ultramicroscopy 86, 159-166, 2001) suggest that associated species of up to 40-mers in size add to the (101) faces. These measurements reflect the sizes of units that both added and desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it will be oriented to some degree in a flowing boundary layer, even at the low flow velocities measured about macromolecule crystals. On Earth, concentration gradient driven flow will maintain a high interfacial concentration, i.e., a high level (essentially that of the bulk solution) of solute association at the interface and higher growth rate. Higher growth rates mean an increased probability that misaligned growth units are trapped by subsequent growth layers before they can be desorbed and try again, or that the desorbing species is more likely to be smaller than the adsorbing species. In microgravity the extended diffusive boundary layer will lower the interfacial concentration. This results in a net dissociation of aggregated species that diffuse in from the bulk solution, i.e., smaller associated species, which are more likely able to make multiple attempts to correctly bind, yielding higher quality crystals.

Pusey, Marc↗
NASA NTRS1991

A definition of the domains Archaea, Bacteria and Eucarya in terms of small subunit ribosomal RNA characteristics

The number of small subunit rRNA sequences is now great enough that the three domains Archaea, Bacteria and Eucarya (Woese et al., 1990) can be reliably defined in terms of their sequence "signatures". Approximately 50 homologous positions (or nucleotide pairs) in the small subunit rRNA characterize and distinguish among the three. In addition, the three can be recognized by a variety of nonhomologous rRNA characters, either individual positions and/or higher-order structural features. The Crenarchaeota and the Euryarchaeota, the two archaeal kingdoms, can also be defined and distinguished by their characteristic compositions at approximately fifteen positions in the small subunit rRNA molecule.

NASA Program Exobiology↗
NASA NTRS2009

Enhancing SERS by Means of Supramolecular Charge Transfer

In a proposed method of sensing small quantities of molecules of interest, surface enhanced Raman scattering (SERS) spectroscopy would be further enhanced by means of intermolecular or supramolecular charge transfer. There is a very large potential market for sensors based on this method for rapid detection of chemical and biological hazards. In SERS, the Raman signals (vibrational spectra) of target molecules become enhanced by factors of the order of 108 when those molecules are in the vicinities of nanostructured substrate surfaces that have been engineered to have plasmon resonances that enhance local electric fields. SERS, as reported in several prior NASA Tech Briefs articles and elsewhere, has remained a research tool and has not yet been developed into a practical technique for sensing of target molecules: this is because the short range (5 to 20 nm) of the field enhancement necessitates engineering of receptor molecules to attract target molecules to the nanostructured substrate surfaces and to enable reliable identification of the target molecules in the presence of interferants. Intermolecular charge-transfer complexes have been used in fluorescence-, photoluminescence-, and electrochemistry-based techniques for sensing target molecules, but, until now, have not been considered for use in SERS-based sensing. The basic idea of the proposed method is to engineer receptor molecules that would be attached to nanostructured SERS substrates and that would interact with the target molecules to form receptor-target supramolecular charge-transfer complexes wherein the charge transfer could be photoexcited.

Wong, Eric↗
NASA NTRS2008

Nanostructures Exploit Hybrid-Polariton Resonances

Nanostructured devices that exploit the hybrid-polariton resonances arising from coupling among photons, phonons, and plasmons are subjects of research directed toward the development of infrared-spectroscopic sensors for measuring extremely small quantities of molecules of interest. The spectroscopic techniques in question are surface enhanced Raman scattering (SERS) and surface enhanced infrared absorption (SEIRA). An important intermediate goal of this research is to increase the sensitivity achievable by these techniques. The basic idea of the approach being followed in this research is to engineer nanostructured devices and thereby engineer their hybrid-polariton resonances to concentrate infrared radiation incident upon their surfaces in such a manner as to increase the absorption of the radiation for SEIRA and measure the frequency shifts of surface vibrational modes. The underlying hybrid-polariton-resonance concept is best described by reference to experimental devices that have been built and tested to demonstrate the concept. The nanostructure of each such device includes a matrix of silicon carbide particles of approximately 1 micron in diameter that are supported on a potassium bromide (KBr) or poly(tetrafluoroethylene) [PTFE] window. These grains are sputter-coated with gold grains of 40-nm size (see figure). From the perspective of classical electrodynamics, in this nanostructure, that includes a particulate or otherwise rough surface, the electric-field portion of an incident electromagnetic field becomes concentrated on the particles when optical resonance conditions are met. Going beyond the perspective of classical electrodynamics, it can be seen that when the resonance frequencies of surface phonons and surface plasmons overlap, the coupling of the resonances gives rise to an enhanced radiation-absorption or -scattering mechanism. The sizes, shapes, and aggregation of the particles determine the frequencies of the resonances. Hence, the task of designing a nanostructure to exhibit the desired radiation-absorption properties translates, in large part, to selecting particle sizes and shapes to obtain the desired enhanced coupling of energy from photons to plasmons and phonons. To broaden the spectral region(s) of enhanced absorption, one would select a distribution of particle sizes and shapes.

Anderson, Mark↗
NASA NTRS2009

Modular and Stochastic Approaches to Molecular Pathway Models of ATM, TGF beta, and WNT Signaling

Deterministic pathway models that describe the biochemical interactions of a group of related proteins, their complexes, activation through kinase, etc. are often the basis for many systems biology models. Low dose radiation effects present a unique set of challenges to these models including the importance of stochastic effects due to the nature of radiation tracks and small number of molecules activated, and the search for infrequent events that contribute to cancer risks. We have been studying models of the ATM, TGF -Smad and WNT signaling pathways with the goal of applying pathway models to the investigation of low dose radiation cancer risks. Modeling challenges include introduction of stochastic models of radiation tracks, their relationships to more than one substrate species that perturb pathways, and the identification of a representative set of enzymes that act on the dominant substrates. Because several pathways are activated concurrently by radiation the development of modular pathway approach is of interest.

Cucinotta, Francis A.↗
NASA NTRS2015

Nanotubular Toughening Inclusions

Conventional toughening agents are typically rubbery materials or small molecular weight molecules, which mostly sacrifice the intrinsic properties of a matrix such as modulus, strength, and thermal stability as side effects. On the other hand, high modulus inclusions tend to reinforce elastic modulus very efficiently, but not the strength very well. For example, mechanical reinforcement with inorganic inclusions often degrades the composite toughness, encountering a frequent catastrophic brittle failure triggered by minute chips and cracks. Thus, toughening generally conflicts with mechanical reinforcement. Carbon nanotubes have been used as efficient reinforcing agents in various applications due to their combination of extraordinary mechanical, electrical, and thermal properties. Moreover, nanotubes can elongate more than 20% without yielding or breaking, and absorb significant amounts of energy during deformation, which enables them to also be an efficient toughening agent, as well as excellent reinforcing inclusion. Accordingly, an improved toughening method is provided by incorporating nanotubular inclusions into a host matrix, such as thermoset and thermoplastic polymers or ceramics without detrimental effects on the matrix's intrinsic physical properties.

Park, Cheol↗
NASA NTRS2017

Nanotubular Toughening Inclusions

Conventional toughening agents are typically rubbery materials or small molecular weight molecules, which mostly sacrifice the intrinsic properties of a matrix such as modulus, strength, and thermal stability as side effects. On the other hand, high modulus inclusions tend to reinforce elastic modulus very efficiently, but not the strength very well. For example, mechanical reinforcement with inorganic inclusions often degrades the composite toughness, encountering a frequent catastrophic brittle failure triggered by minute chips and cracks. Thus, toughening generally conflicts with mechanical reinforcement. Carbon nanotubes have been used as efficient reinforcing agents in various applications due to their combination of extraordinary mechanical, electrical, and thermal properties. Moreover, nanotubes can elongate more than 20% without yielding or breaking, and absorb significant amounts of energy during deformation, which enables them to also be an efficient toughening agent, as well as excellent reinforcing inclusion. Accordingly, an improved toughening method is provided by incorporating nanotubular inclusions into a host matrix, such as thermoset and thermoplastic polymers or ceramics without detrimental effects on the intrinsic physical properties of the matrix.

Park, Cheol↗
NASA NTRS1997

New Anti-Corrosive Coatings with Resin-Bonded Polyaniline and Related Electroactive Groups

It is already known that polyaniline (an electroactive polymer) functions as a corrosion inhibitor for steel and in view of the fact that it is known to perform in the presence of hydrochloric acid, it has been considered likely that it may be useful to NASA for protecting launch structures at KSC which are exposed to not only continual ocean-side salt spray but also to hydrochloric acid at the times that solid-fuel boosters are fired. The currently used zinc-rich silicate-bonded coating is not wholly protective against the hydrochloric acid. Water pollution from zinc salts is another concern. Other earlier and concurrent NASA sponsored projects have been focussed on polyaniline specifically. Our project, administered for NASA by Dr. K. Thompson of KSC and these more-specifically polyaniline-related projects are included in a CRADA coordinated by Dr. F. Via of Akzo Nobel. A parallel project at Polytechnic under Prof K. Levon concentrated more specifically on polyaniline with various dopants. Our exploratory project reported herein was aimed at broadening the range of such corrosion inhibitors, to give protective paint compounders a wider latitude for adding corrosion inhibitors having polyaniline-like performance, and thus we diverged in several probing directions from polyaniline. Our working hypothesis was that physical variants of polyaniline, such as supported formulations on pigments or carriers, and chemical variants of polyaniline, including those having no electroconductive character, may have enhanced anticorrosion activity. We also hypothesized that small (non-polymeric) molecules having structures related to those occurring in polyaniline, may be active as corrosion inhibitors. We did preliminary testing, using an ASTM salt spray method at a nearby commercial paint testing laboratory. Our most interesting findings were that a non-electroconductive meta-isomer of polyaniline showed some corrosion activity, suggesting that the features of the polyaniline molecule associated with conductivity are not necessary for the anticorrosion action. Also, signtficantly, small molecular weight aromatic diamines and diimines resembling the reduced and the oxidized repeating unit in polyaniline showed an interesting degree of anticorrosive activity, suggesting that the polymeric feature of polyaniline is not necessary for anticorrosion action.

Weil, Edward D.↗
NASA NTRS1992

Scattering of infrared radiation by dust in NGC 7023 and NGC 2023

The contribution of scattered light to the total nebular emission is determined on the basis of linear polarization measurements at 1.25, 1.65, and 2.2 microns of the visual reflection nebulae NGC 7023 and NGC 2023. The percentage polarization of NGC 7023 slowly increases from 0.3 to 1 micron, with peak polarizations of up to 26 percent at 1.25 micron, then rapidly decreases, with values of 4-7 percent at 2.2 microns. This is interpreted as implying that scattered starlight contributes most to the SW emission, while unpolarized emission from small grains or large molecules dominates at longer wavelengths. IR polarization and surface brightness measurements are combined to derive the intensity of scattered light, which is then compared with scattering models. While the near-IR emission of both NGC 2023 and NGC 7023 is dominated by small-grain or large-molecule emission, IR scattered light plays a larger role in NGC 2023 than in NGC 7023.

Sellgren, K.↗
NASA NTRS1996

Infrared emission spectra of candidate interstellar aromatic molecules

Interstellar dust is responsible, through surface reactions, for the creation of molecular hydrogen, the main component of the interstellar clouds in which new stars form. Intermediate between small, gas-phase molecules and dust are the polycyclic aromatic hydrocarbons (PAHs). Such molecules could account for 2-30% of the carbon in the Galaxy, and may provide nucleation sites for the formation of carbonaceous dust. Although PAHs have been proposed as the sources of the unidentified infrared emission bands that are observed in the spectra of a variety of interstellar sources, the emission characteristics of such molecules are still poorly understood. Here we report laboratory emission spectra of several representative PAHs, obtained in conditions approximating those of the interstellar medium, and measured over the entire spectral region spanned by the unidentified infrared bands. We find that neutral PAHs of small and moderate size can at best make only a minor contribution to these emission bands. Cations of these molecules, as well as much larger PAHs and their cations, remain viable candidates for the sources of these bands.

Non-NASA Center↗