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At least 217 records · Page 12

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NASA NTRS2011

Process-Hardened, Multi-Analyte Sensor for Characterizing Rocket Plume Constituents

A multi-analyte sensor was developed that enables simultaneous detection of rocket engine combustion-product molecules in a launch-vehicle ground test stand. The sensor was developed using a pin-printing method by incorporating multiple sensor elements on a single chip. It demonstrated accurate and sensitive detection of analytes such as carbon dioxide, carbon monoxide, kerosene, isopropanol, and ethylene from a single measurement. The use of pin-printing technology enables high-volume fabrication of the sensor chip, which will ultimately eliminate the need for individual sensor calibration since many identical sensors are made in one batch. Tests were performed using a single-sensor chip attached to a fiber-optic bundle. The use of a fiber bundle allows placement of the opto-electronic readout device at a place remote from the test stand. The sensors are rugged for operation in harsh environments.

Goswami, Kisholoy↗

NASA NTRS2021

Direct Measurements of Infrared Intensities of HCN and H2O + HCN Ices for Laboratory and Observational Astrochemistry

Hydrogen cyanide (HCN) is found in a wide variety of extraterrestrial environments within and beyond the solar system, and for that reason laboratory spectroscopists have studied this compound in many spectral regions, including the infrared (IR). However, one aspect that remains to be investigated is the intrinsic IR spectral intensities of solid HCN as opposed to relative band strengths, intrinsic intensities being needed to measure HCN abundances. Here we report measurements of IR absorption coefficients and band strengths, along with supporting refractive indices and densities, of both amorphous and crystalline HCN at two temperatures, one for interstellar work and one more relevant to the outer solar system. Spectra are presented at both temperatures, along with optical constants that can be used in numerical models. Despite widespread and longstanding interest in and investigations of solid HCN, this is the first time that the properties we are reporting have been measured in a single laboratory, avoiding the need for estimates or to combine results from various authors. We find that our measured band strength of ~1 × 1017 cm molecule1 for the CN vibration of HCN, in both amorphous HCN and in an H2O-rich ice, is substantially higher than an earlier estimate. Unless errors of 100% can be tolerated then our new value requires a rescaling of earlier work. Our results shed light on why HCN and other nitriles have been so difficult to identify in the solid state, in contrast to their many detections in the gas phase.

astrochemistry – methods: laboratory – solid state↗

NASA NTRS2021

Direct Measurements of Infrared Intensities of HCN and H2O + HCN Ices for Laboratory and Observational Astrochemistry

astrochemistry – methods: laboratory – solid state↗

NASA NTRS2017

Exploring Connectivity in Sequence Space of Functional RNA

Emergence of replicable genetic molecules was one of the marking points in the origin of life, evolution of which can be conceptualized as a walk through the space of all possible sequences. A theoretical concept of fitness landscape helps to understand evolutionary processes through assigning a value of fitness to each genotype. Then, evolution of a phenotype is viewed as a series of consecutive, single-point mutations. Natural selection biases evolution toward peaks of high fitness and away from valleys of low fitness. whereas neutral drift occurs in the sequence space without direction as mutations are introduced at random. Large networks of neutral or near-neutral mutations on a fitness landscape, especially for sufficiently long genomes, are possible or even inevitable. Their detection in experiments, however, has been elusive. Although a few near-neutral evolutionary pathways have been found, recent experimental evidence indicates landscapes consist of largely isolated islands. The generality of these results, however, is not clear, as the genome length or the fraction of functional molecules in the genotypic space might have been insufficient for the emergence of large, neutral networks. Thorough investigation on the structure of the fitness landscape is essential to understand the mechanisms of evolution of early genomes. RNA molecules are commonly assumed to play the pivotal role in the origin of genetic systems. They are widely believed to be early, if not the earliest, genetic and catalytic molecules, with abundant biochemical activities as aptamers and ribozymes, i.e. RNA molecules capable, respectively, to bind small molecules or catalyze chemical reactions. Here, we present results of our recent studies on the structure of the sequence space of RNA ligase ribozymes selected through in vitro evolution. Several hundred thousands of sequences active to a different degree were obtained by way of deep sequencing. Analysis of these sequences revealed several large clusters defined such that every sequence in a cluster can be reached from any other sequence in the same cluster through a series of single point mutations. Sequences in a single cluster appear to adopt more than one secondary structure. The mechanism of refolding within a single cluster was examined. To shed light on possible evolutionary paths in the space of ribozymes, the connectivity between clusters was investigated. The effect of length of RNA molecules on the structure of the fitness landscape and possible evolutionary paths was examined by way of comparing functional sequences of 20 and 80 nucleobases in length. It was found that sequences of different lengths shared secondary structure motifs that were presumed responsible for catalytic activity, with increasing complexity and global structural rearrangements emerging in longer molecules.

Wei, Chenyu↗

NASA NTRS1996

Single residue substitutions that change the gating properties of a mechanosensitive channel in Escherichia coli

MscL is a channel that opens a large pore in the Escherichia coli cytoplasmic membrane in response to mechanical stress. Previously, we highly enriched the MscL protein by using patch clamp as a functional assay and cloned the corresponding gene. The predicted protein contains a largely hydrophobic core spanning two-thirds of the molecule and a more hydrophilic carboxyl terminal tail. Because MscL had no homology to characterized proteins, it was impossible to predict functional regions of the protein by simple inspection. Here, by mutagenesis, we have searched for functionally important regions of this molecule. We show that a short deletion from the amino terminus (3 amino acids), and a larger deletion of 27 amino acids from the carboxyl terminus of this protein, had little if any effect in channel properties. We have thus narrowed the search of the core mechanosensitive mechanism to 106 residues of this 136-amino acid protein. In contrast, single residue substitutions of a lysine in the putative first transmembrane domain or a glutamine in the periplasmic loop caused pronounced shifts in the mechano-sensitivity curves and/or large changes in the kinetics of channel gating, suggesting that the conformational structure in these regions is critical for normal mechanosensitive channel gating.

Non-NASA Center↗

NASA NTRS1981

Rate of H2 formation on amorphous grains

The rate of formation of molecular hydrogen from hydrogen atoms adsorbed on amorphous grains taken to represent interstellar dust grains is analyzed. Following a brief review of the structure and thermodynamics of amorphous grains and the evidence that interstellar grains are indeed amorphous, consideration is given to the mechanism of formation of H2 molecules by the impact of H atoms on grains with adsorbed H atoms, and it is concluded that on amorphous grains, molecule formation will only occur if H atoms are adsorbed within a distance on the order of 10 A of each other. Rates of H2 formation on single crystal and polycrystalline grains are then calculated and compared with those for amorphous grains, and it is shown that, except for certain temperatures and high H atom densities, the rates of H2 formation on polycrystalline and amorphous grains are up to a few orders of magnitude lower than on single crystals. The results suggest that amorphous grains will lead to H2 clouds with irregular and sharply delineated features in contrast to the more uniform clouds formed on crystalline grains.

Smoluchowski, R.↗

NASA NTRS1991

Growth of thin films of organic nonlinear optical materials by vapor growth processes - An overview and examination of shortfalls

Research on the growth of second- and third-order nonlinear optical (NLO) organic thin film by vapor deposition is reviewed. Particular attention is given to the experimental methods for growing thin films of p-chlorophenylurea, diacetylenes, and phthalocyanines; characteristics of the resulting films; and approaches for advancing thin film technology. It is concluded that the growth of NLO thin films by vapor processes is a promising method for the fabrication of planar waveguides for nonlinear optical devices. Two innovative approaches are proposed including a method of controlling the input beam frequency to maximize nonlinear effects in thin films and single crystals, and the alternate approach to the molecular design of organic NLO materials by increasing the transition dipole moment between ground and excited states of the molecule.

Frazier, D. O.↗

NASA NTRS1997

Optical and Atomic Force Microscopy Characterization of PbI2 Quantum Dots

Lead iodide (PbI2) clusters were synthesized from the chemical reaction of NaI (or KI) with Pb(NO3)2 in H2O, D2O, CH3OH, and C3H7OH media. The observation of the absorption features above 350 nm with the help of integrating sphere accessory strongly suggests the quantum dot formation of PbI2 in solution. Spectral comparison between the synthesized PbI2 clusters in solution and PbI2 nanophase by impregnation of PbI2 in four different pore-sized porous silica indicates that the PbI2 cluster size in solution is less than 2.5 nm in lateral dimension. Atomic force microscopy (AFM) measurements show that the PbL clusters deposited onto three different molecularly flat surfaces are single-layered. The measured height is 1.0 - 0.1 nm. The swollen layer thickness can be attributed to the intralayer contraction from the strong lateral interaction among PbI2 molecules, which is supported by ab initio calculation. Raman scattering measurement of LO and TO modes of PbI2 in bulk and in the confined state were also conducted in 50-150 cu cm region. The observed three bands at 74, %, 106 1/cm are assigned to TO2, LO2, and LO, mode, respectively. The relatively small red-shift in LO modes may be caused by the surface phonon polaritons of PbI2 nanophase in the porous silica.

Mu, R.↗

NASA NTRS2000

Fluid Physics and Macromolecular Crystal Growth in Microgravity

The molecular structure of biological macromolecules is important in understanding how these molecules work and has direct application to rational drug design for new medicines and for the improvement and development of industrial enzymes. In order to obtain the molecular structure, large, well formed, single macromolecule crystals are required. The growth of macromolecule crystals is a difficult task and is often hampered on the ground by fluid flows that result from the interaction of gravity with the crystal growth process. One such effect is the bulk movement of the crystal through the fluid due to sedimentation. A second is buoyancy driven convection close to the crystal surface. On the ground the crystallization process itself induces both of these flows. Buoyancy driven convection results from density differences between the bulk solution and fluid close to the crystal surface which has been depleted of macromolecules due to crystal growth. Schlieren photograph of a growing lysozyme crystal illustrating a 'growth plume' resulting from buoyancy driven convection. Both sedimentation and buoyancy driven convection have a negative effect on crystal growth and microgravity is seen as a way to both greatly reduce sedimentation and provide greater stability for 'depletion zones' around growing crystals. Some current crystal growth hardware however such as those based on a vapor diffusion techniques, may also be introducing unwanted Marangoni convection which becomes more pronounced in microgravity. Negative effects of g-jitter on crystal growth have also been observed. To study the magnitude of fluid flows around growing crystals we have attached a number of different fluorescent probes to lysozyme molecules. At low concentrations, less than 40% of the total protein, the probes do not appear to effect the crystal growth process. By using these probes we expect to determine not only the effect of induced flows due to crystal growth hardware design but also hope to optimize crystallization hardware so that destructive flows are minimized both on the ground and in microgravity.

Pusey, M.↗

NASA NTRS1978

Monte Carlo solution of Boltzmann equation for a simple model of highly nonequilibrium diatomic gases - Translational rotational energy relaxation

Theoretical results pertaining to internally excited translational-rotational energy relaxation in a spatially uniform diatomic gas far removed from solid boundaries are obtained by solving the Boltzmann equation by means of the Monte Carlo direct simulation method. The analysis is based on calculations involving three different types of initial conditions: equilibrium, nonequilibrium-equipartition (i.e., equipartition is satisfied, but the distributions are perturbed), and nonequilibrium-nonequipartition (i.e., both equipartition and the distributions are perturbed). Results of monatomic-gas simulations are also included to facilitate comparisons with the coupled translational-rotational relaxation simulations, and some simulations for a normal shock-wave structure are briefly examined. The results show that: (1) single-step transitions are the significant mechanisms of intermodal energy transfer; (2) translational-rotational transitions are coupled most efficiently for low-lying states of rotationally excited molecules and least efficiently for highly rotationally excited molecules; and (3) relaxation occurs via a successive set of distributions that are not Maxwell-Boltzmann (nonlocal Maxwellian).

Yoshikawa, K. K.↗

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 NTRS1990

Impact fracture experiments simulating interstellar grain-grain collisions

Oxide and silicate grains condensing during the early phases of the formation of the solar system or in the outflow of stars are exposed to high partial pressures of the low-z elements H, C, N and O and their simple gaseous compounds. Though refractory minerals are nominally anhydrous and non-carbonate, if they crystallize in the presence of H2O, N2 and CO or CO2 gases, they dissolve traces of the gaseous components. The question arises: How does the presence of dissolved gases or gas components manifest itself when grain-grain collisions occur. What are the gases emitted when grains are shattered during a collision event. Researchers report on fracture experiments in ultrahigh vacuum (UHV, approximately less than 10 to the -8th power mbar) designed to measure (by means of a quadrupole mass spectrometer, QMS, with microns to ms time resolution) the emission of gases and vapors during and after impact (up to 1.5 sec). Two terrestrial materials were chosen which represent structural and compositional extremes: olivine (San Carlos, AZ), a densely packed Mg-Fe(2+) silicate from the upper mantle, available as 6 to 12 mm single crystals, and obsidian (Oregon), a structurally open, alkaline-SiO2-rich volcanic glass. In the olivine crystals OH- groups have been identified spectroscopically, as well as H2 molecules. Obsidian is a water-rich glass containing OH- besides H2O molecules. Olivine from the mantle often contains CO2, either as CO2-rich fluid in fluid inclusions or structurally dissolved or both. By analogy to synthetic glasses CO2 in the obsidian may be present in form of CO2 molecules in voids of molecular dimensions, or as carbonate anions, CO3(2-). No organic molecules have been detected spectroscopically in either material. Results indicate that refractory oxide/silicates which contain dissolved traces of the H2O and CO/CO2 components but no spectroscopically detectable traces of organics may release complex H-C-O (possibly H-C-N-O) molecules upon fracture, plus metal vapor. This points: (1) at complex reaction mechanisms between dissolved H2O, CO/CO2 (and N2) components within the mineral structure or during fracture, and (2) at the possibility that similar emission processes occur following grain-grain collisions in interstellar dust clouds.

Freund, Friedemann↗

NASA NTRS1998

Analyses at High Spatial Resolution of Organic Molecules in Extraterrestrial Samples: Two-Step Laser Mass Spectrometry: Search for Polycyclic Aromatic Hydrocarbons in Antarctic Meteorite and Micrometeorite Samples

Perhaps the best way to summarize the past three-year grant period is to cite the publications and present a brief synopsis of each: 1. "Indigenous Polycyclic Aromatic Hydrocarbon Molecules in Circumstellar Graphite Grains." Bulk C-12/C-13 isotope ratios observed in some graphite grains extracted from primitive meteorites point strongly to a circumstellar origin. By applying our technique of microprobe two-step laser desorption laser ionization mass spectrometry ((mu)L(sup 2)MS) to individual circumstellar graphite grains we have measured the C-12/C-13 isotope ratio of various polycyclic aromatic hydrocarbons (PAHS) found in these grains. 2. "Deuterium Enrichments in Cluster IDPS," Large enrichments in the D/H isotope ratios in IDPs likely arise from the preservation of presolar molecules. 3. "Evidence for thermalization of surface-disorder molecules at heating rates of 10(exp 8) K/s". A careful study of the ((mu)L(sup 2)MS) of aniline-d(sub 7) from a single-crystal surface (0001) of sapphire (al2O3) shows that all measured properties are consistent with a thermal mechanism for desorption. 4. "Search for past life on Mars; possible relic biogenic activity in Martian meteorite ALH 84001. The authors examined the Martian meteorite ALH 84001 and found several lines of evidence compatible with existence of past primitive (single-cell) life on early Mars. 5. "Microprobe two-step laser mass spectrometry as an analytical tool for meteorite samples". THis paper presents a comprehensive review of (mu)L(sup 2)MS and how this technique can be applied to meteoritic samples. 6. "Indigenous polycyclic aromatic hydrocarbons in circumstellar graphite grains from primitive meteorites". The C-12/C-13 isotope ratios were measured for PAHs in a total of 89 spherical graphite grains. 7. "Observation of indigenous polycyclic aromatic hydrocarbons in "Giant" carbonaceous antarctic micrometeorites." The (mu)L(sup 2)MS method was used to establish the nature and distribution of PAHs in fragments of fifteen (approx. 200 microns) carbonaceous antarctic micrometeorites (AMMs). 8. "Evidence for the extraterrestrial origin of polycyclic aromatic hydrocarbons in the Martian meteorite ALH 84001" We have undertaken additional contamination studies of ALH 84001.

Zare, Richard N.↗

NASA NTRS1995

Observations of chemical processing in the circumstellar environment

High resolution interferometer and single-dish observations of young, deeply embedded stellar systems reveal a complex chemistry in the circumstellar environments of low to intermediate mass stars. Depletions of gas-phase molecules, grain mantle evaporation, and shock interactions actively drive chemical processes in different regions around young stars. We present results for two systems, IRAS 05338-0624 and NCG 1333 IRAS 4, to illustrate the behavior found and to examine the physical processes at work.

NASA Program Exobiology↗

NASA NTRS2011

Initiating Molecular Growth in the Interstellar Medium via Dimeric Complexes of Observed Ions and Molecules

A feasible initiation step for particle growth in the interstellar medium (ISM) is simulated by means of ab quantum chemistry methods. The systems studied are dimer ions formed by pairing nitrogen containing small molecules known to exist in the ISM with ions of unsaturated hydrocarbons or vice versa. Complexation energies, structures of ensuing complexes and electronic excitation spectra of the encounter complexes are estimated using various quantum chemistry methods. Moller-Plesset perturbation theory (MP2, Z-averaged perturbation theory (ZAP2), coupled cluster singles and doubles with perturbative triples corrections (CCSD(T)), and density functional theory (DFT) methods (B3LYP) were employed along with the correlation consistent cc-pVTZ and aug-cc-pVTZ basis sets. Two types of complexes are predicted. One type of complex has electrostatic binding with moderate (7-20 kcal per mol) binding energies, that are nonetheless significantly stronger than typical van der Waals interactions between molecules of this size. The other type of complex develops strong covalent bonds between the fragments. Cyclic isomers of the nitrogen containing complexes are produced very easily by ion-molecule reactions. Some of these complexes show intense ultraviolet visible spectra for electronic transitions with large oscillator strengths at the B3LYP, omegaB97, and equations of motion coupled cluster (EOM-CCSD) levels. The open shell nitrogen containing carbonaceous complexes especially exhibit a large oscillator strength electronic transition in the visible region of the electromagnetic spectrum.

Bera, Partha P.↗

NASA NTRS1994

Alpha-helical hydrophobic polypeptides form proton-selective channels in lipid bilayers

Proton translocation is important in membrane-mediated processes such as ATP-dependent proton pumps, ATP synthesis, bacteriorhodopsin, and cytochrome oxidase function. The fundamental mechanism, however, is poorly understood. To test the theoretical possibility that bundles of hydrophobic alpha-helices could provide a low energy pathway for ion translocation through the lipid bilayer, polyamino acids were incorporated into extruded liposomes and planar lipid membranes, and proton translocation was measured. Liposomes with incorporated long-chain poly-L-alanine or poly-L-leucine were found to have proton permeability coefficients 5 to 7 times greater than control liposomes, whereas short-chain polyamino acids had relatively little effect. Potassium permeability was not increased markedly by any of the polyamino acids tested. Analytical thin layer chromatography measurements of lipid content and a fluorescamine assay for amino acids showed that there were approximately 135 polyleucine or 65 polyalanine molecules associated with each liposome. Fourier transform infrared spectroscopy indicated that a major fraction of the long-chain hydrophobic peptides existed in an alpha-helical conformation. Single-channel recording in both 0.1 N HCl and 0.1 M KCl was also used to determine whether proton-conducting channels formed in planar lipid membranes (phosphatidylcholine/phosphatidylethanolamine, 1:1). Poly-L-leucine and poly-L-alanine in HCl caused a 10- to 30-fold increase in frequency of conductive events compared to that seen in KCl or by the other polyamino acids in either solution. This finding correlates well with the liposome observations in which these two polyamino acids caused the largest increase in membrane proton permeability but had little effect on potassium permeability. Poly-L-leucine was considerably more conductive than poly-L-alanine due primarily to larger event amplitudes and, to a lesser extent, a higher event frequency. Poly-L-leucine caused two populations of conductive events, one in the 0.1-0.5 pA range, and one in the 1.0-5.0 pA range, whereas nearly all events caused by poly-L-alanine were in the 0.1-0.5 pA range at an applied voltage of +60 mV. The channel-like activity appeared to switch between conductive and nonconductive states, with most open-times in the range of 50-200 ms. We conclude that hydrophobic polyamino acids produce proton-conducting defects in lipid bilayers that may be used to model functional proton channels in biological membranes.

NASA Discipline Exobiology↗

NASA NTRS1993

Hypervelocity impact survivability experiments for carbonaceous impactors

We performed a series of hypervelocity impact experiments using carbon-bearing impactors (diamond, graphite, fullerenes, phthalic acid crystals, and Murchison meteorite) into Al plate at velocities between 4.2 and 6.1 km/s. These tests were made to do the following: (1) determine the survivability of carbon forms and organize molecules in low hypervelocity impact; (2) characterize carbonaceous impactor residues; and (3) determine whether or not fullerenes could form from carbonaceous impactors, under our experimental conditions, or survive as impactors. An analytical protocol of field emission SEM imagery, SEM-EDX, laser Raman spectroscopy, single and 2-stage laser mass spectrometry, and laser induced fluorescence (LIF) found the following: (1) diamonds did not survive impact at 4.8 km/s, but were transformed into various forms of disordered graphite; (2) intact, well-ordered graphite impactors did survive impact at 5.9 km/sec, but were only found in the crater bottom centers; the degree of impact-induced disorder in the graphite increases outward (walls, rims, ejecta); (3) phthalic acid crystals were destroyed on impact (at 4.2 km/s, although a large proportion of phthalic acid molecules did survive impact); (4) fullerenes did not form as products of carbonaceous impactors (5.9 - 6.1 km/s, fullerene impactor molecules mostly survived impact at 5.9 km/s; and (5) two Murchison meteorite samples (launched at 4.8 and 5.9 km/s) show preservation of some higher mass polycyclic aromatic hydrocarbons (PAHs) compared with the non-impacted sample. Each impactor type shows unique impactor residue morphologies produced at a given impact velocity. An expanded methodology is presented to announce relatively new analytical techniques together with innovative modifications to other methods that can be used to characterize small impact residues in LDEF craters, in addition to other acquired extraterrestrial samples.

Bunch, T. E.↗

NASA NTRS1995

Ab Initio Characterization of Triatomic Bromine Molecules of Potential Interest in Stratospheric Chemistry

The equilibrium structures, harmonic vibrational frequencies, quadratic force fields, dipole moments, and IR intensities of several triatomic bromine compounds of known or potential importance in stratospheric ozone depletion chemistry have been determined using the CCSD(T) electron correlation method in conjunction with a basis set of triple zeta double polarized (TZ2P) quality. Specifically, the molecules included in the present study are HOBr, HBrO, FOBr, FBrO, BrNO, BrON, Br2O, BrBrO, BrCN, BrNC, ClOBr, ClBrO, and BrClO. Very accurate isomeric energy differences have also been determined at the CCSD(T) level with atomic natural orbital basis sets that include through g-type functions. In most cases, the isomer with a normal neutral Lewis dot structure is the lowest energy form, with the single exception that FBRO is predicted to be 11.1 kcal/mol (0 K) lower in energy than FOBr. In all cases, however, the hypervalent isomer is more stable relative to the isomer with a normal Lewis dot structure as compared to the chlorine analogs. Consistent with this observation, the energy of the last three molecules given above increases in the order ClOBr less than ClBrO less than BrClO. The CCSD(T)/TZ2P geometries and vibrational frequencies are in good agreement with the available experimental data. Heats of formation are determined for all species using a combination of theoretical isomeric, homodesmic, and isodesmic reaction energies. The accuracy of these quantities is ultimately dependent on the reliability of the experimental heat of formation of HOBr.

Lee. Timothy J.↗