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At least 253 records · Page 14

Hydrous pyrolysis of polycyclic aromatic hydrocarbons and implications for the origin of PAH in hydrothermal petroleum

Polycyclic aromatic hydrocarbons (PAH) are found at high concentrations in thermally altered organic matter and hydrothermally generated petroleum from sediment-covered seafloor hydro-thermal systems. To better understand the factors controlling the occurrence of PAH in thermally altered environments, the reactivities of two PAH, phenanthrene and anthracene, were investigated in hydrothermal experiments. The compounds were heated with water at 330 degrees C in sealed reaction vessels for durations ranging from 1 to 17 days. Iron oxide and sulfide minerals, formic acid, or sodium for-mate were included in some experiments to vary conditions within the reaction vessel. Phenanthrene was unreactive both in water alone and in the presence of minerals for up to 17 days, while anthracene was partially hydrogenated (5-10%) to di- and tetrahydroanthracene. In the presence of 6-21 vol % formic acid, both phenanthrene and anthracene reacted extensively to form hydrogenated and minor methylated derivatives, with the degree of hydrogenation and methylation increasing with the amount of formic acid. Phenanthrene was slightly hydrogenated in sodium formate solutions. The hydrogenation reactions could be readily reversed; heating a mixture of polysaturated phenanthrenes resulted in extensive dehydrogenation (aromatization) after 3 days at 330 degrees C. While the experiments demonstrate that reaction pathways for the hydrogenation of PAH under hydrothermal conditions exist, the reactions apparently require higher concentrations of H2 than are typical of geologic settings. The experiments provide additional evidence that PAH may be generated in hydrothermal systems from progressive aromatization and dealkylation of biologically derived polycyclic precursors such as steroids and terpenoids. Furthermore, the results indicate that PAH initially present in sediments or formed within hydrothermal systems are resistant to further thermal degradation during hydrothermal alteration.

NASA Discipline Exobiology↗

Photochemical cycloaddition reactions of cyanoacetylene and dicyanoacetylene

Photolysis of cyanoacetylene with 185- or 206-nm light yields 1,3,5-tricyanobenzene while 254-nm radiation yields a mixture of tetracyanocyclooctatetraenes, 1,2,4- and 1,3,5-tricyanobenzene. A polymer of cyanoacetylene is the major photoproduct. 1,3,5-Tricarbomethoxybenzene was the only photoproduct identified from the irradiation of methyl propiolate at 254 nm. Mono-, di-, and tricyanobenzenes are formed by irradiation of mixtures of acetylene and cyanoacetylene at 185, 206, and 254 nm along with trace amounts of cyclooctatetraenes. No photoadducts were detected on photolysis of mixtures of cyanoacetylene and CO or HCN. The tetracyanocyclooctatetraene structures were established by UV, MS, and NMR analyses. The 1H NMR of the product mixture exhibited a singlet at delta 7.028 consistent with either 1 or 2 and two singlets at delta 6.85 and 6.91 assigned to 3. Photolysis of mixtures of dicyanoacetylene and acetylene with either 185- or 206-nm light yielded 1,2-dicyanobenzene and (E,Z)-1-buten-3-yne-1,4-dicarbonitrile. These products were also obtained using 254-nm light along with a mixture of tetracyanocyclooctatetraenes. The same three singlets were observed in this product mixture as were observed in the tetracyanocyclooctatetraenes obtained from cyanoacetylene. From this observation it was concluded that the delta 7.02 signal is due to 2 and not 1. The photolysis of cyanoacetylene and dicyanoacetylene in the presence of ethylene with 185-nm light yields 1-cyanocylobutene and 1,2-dicyanocyclobutene, respectively. 2-Cyanobutadiene and 2,3-dicyanobutadiene are the photoproducts with 254-nm light. Reaction pathways are proposed to explain these findings.

NASA Discipline Exobiology↗

Permeability of membranes to amino acids and modified amino acids: mechanisms involved in translocation

The amino acid permeability of membranes is of interest because they are one of the key solutes involved in cell function. Membrane permeability coefficients (P) for amino acid classes, including neutral, polar, hydrophobic, and charged species, have been measured and compared using a variety of techniques. Decreasing lipid chain length increased permeability slightly (5-fold), while variations in pH had only minor effects on the permeability coefficients of the amino acids tested in liposomes. Increasing the membrane surface charge increased the permeability of amino acids of the opposite charge, while increasing the cholesterol content decreased membrane permeability. The permeability coefficients for most amino acids tested were surprisingly similar to those previously measured for monovalent cations such as sodium and potassium (approximately 10(-12)-10(-13) cm s-1). This observation suggests that the permeation rates for the neutral, polar and charged amino acids are controlled by bilayer fluctuations and transient defects, rather than partition coefficients and Born energy barriers. Hydrophobic amino acids were 10(2) more permeable than the hydrophilic forms, reflecting their increased partition coefficient values. External pH had dramatic effects on the permeation rates for the modified amino acid lysine methyl ester in response to transmembrane pH gradients. It was established that lysine methyl ester and other modified short peptides permeate rapidly (P = 10(-2) cm s-1) as neutral (deprotonated) molecules. It was also shown that charge distributions dramatically alter permeation rates for modified di-peptides. These results may relate to the movement of peptides through membranes during protein translocation and to the origin of cellular membrane transport on the early Earth.

Review↗

Layered double hydroxide stability. 1. Relative stabilities of layered double hydroxides and their simple counterparts

Solutions containing di- and trivalent metal chlorides [M(II) = Mg2+, Zn2+, Co2+, Ni2+, Mn2+; M(III) = Al3+, Fe3+] were titrated with NaOH to yield hydrotalcite-like layered double hydroxides (LDH), [[M(II)]1-x[M(III)]x(OH)2][Cl]x yH2O, by way of M(III) hydroxide/hydrous oxide intermediates. Analysis of the resultant titration curves yields nominal solubility constants for the LDH. The corresponding LDH stabilities are in the order Mg < Mn < Co approximately Ni < Zn for M(II) and Al < Fe for M(III). The stability of LDH relative to the separate metal hydroxides/hydrous oxides is discussed.

Non-NASA Center↗

Polyimides Containing Fluorine and Phosphorus for Potential Space Applications

As part of an effort to develop low color, ultraviolet (UV) radiation and atomic oxygen resistant polyimides for potential space applications, a novel diamine containing fluorine and phosphorus was synthesized and used to prepare polyimides. The approach was to combine attributes from colorless, UV resistant polyimides and atomic oxygen (AO) resistant polymers into a single material. Preparation of colorless polyimides has focused on minimization of charge transfer complex formation by incorporation of bulky substituents and disrupting conjugation by using meta-catenated monomers. AO resistant polymer technology development has focused on placing phenylphosphine oxide groups into the backbone of aromatic polymers. However, polyimides prepared utilizing this approach thus far have all exhibited significant color. Thus in an attempt to combine these features in a polyimide a new diamine, bis(3-aminophenyl)-3,5-di(trifluoromethyl)phenylphosphine oxide (TFMDA) was synthesized and used to prepare polyimides. The polyimides were cast into films and characterized for physical and mechanical properties, optical transmission and AO and UV resistance.

Connell, John W.↗

Radiation Modeling with Direct Simulation Monte Carlo

Improvements in the modeling of radiation in low density shock waves with direct simulation Monte Carlo (DSMC) are the subject of this study. A new scheme to determine the relaxation collision numbers for excitation of electronic states is proposed. This scheme attempts to move the DSMC programs toward a more detailed modeling of the physics and more reliance on available rate data. The new method is compared with the current modeling technique and both techniques are compared with available experimental data. The differences in the results are evaluated. The test case is based on experimental measurements from the AVCO-Everett Research Laboratory electric arc-driven shock tube of a normal shock wave in air at 10 km/s and .1 Torr. The new method agrees with the available data as well as the results from the earlier scheme and is more easily extrapolated to di erent ow conditions.

Carlson, Ann B.↗

Extracellular signal-regulated kinases 1 and 2 activation in endothelial cells exposed to cyclic strain

The aim of this study was to determine whether extracellular signal-regulated kinases 1/2 (ERK1/ERK2) are activated and might play a role in enhanced proliferation and morphological change induced by strain. Bovine aortic endothelial cells (BAEC) were subjected to an average of 6 or 10% strain at a rate of 60 cycles/min for up to 4 h. Cyclic strain caused strain- and time-dependent phosphorylation and activation of ERK1/ERK2. Peak phosphorylation and activation of ERK1/ERK2 induced by 10% strain were at 10 min. A specific ERK1/ERK2 kinase inhibitor, PD-98059, inhibited phosphorylation and activation of ERK1/ERK2 but did not inhibit the increased cell proliferation and cell alignment induced by strain. Treatment of BAEC with 2,5-di-tert-butyl-1, 4-benzohydroquinone, to deplete inositol trisphosphate-sensitive calcium storage, and gadolinium chloride, a Ca2+ channel blocker, did not inhibit the activation of ERK1/ERK2. Strain-induced ERK1/ERK2 activation was partly inhibited by the protein kinase C inhibitor calphostin C and completely inhibited by the tyrosine kinase inhibitor genistein. These data suggest that 1) ERK1/ERK2 are not critically involved in the strain-induced cell proliferation and orientation, 2) strain-dependent activation of ERK1/ERK2 is independent of intracellular and extracellular calcium mobilization, and 3) protein kinase C activation and tyrosine kinase regulate strain-induced activation of ERK1/ERK2.

NASA Discipline Cell Biology↗

Multiple receptor subtypes mediate the effects of serotonin on rat subfornical organ neurons

The subfornical organ (SFO) receives significant serotonergic innervation. However, few reports have examined the functional effects of serotonin on SFO neurons. This study characterized the effects of serotonin on spontaneously firing SFO neurons in the rat brain slice. Of 31 neurons tested, 80% responded to serotonin (1-100 microM) with either an increase (n = 15) or decrease (n = 10) in spontaneous activity. Responses to serotonin were dose dependent and persisted after synaptic blockade. Excitatory responses could also be mimicked by the 5-hydroxytryptamine (5-HT)2A/2C receptor agonist 2,5-dimethoxy-4-iodoamphetamine (DOI; 1-10 microM) and could be blocked by the 5-HT2A/2C-receptor antagonist LY-53,857 (10 microM). LY-53,857 unmasked inhibitory responses to serotonin in 56% of serotonin-excited cells tested. Serotonin-inhibited cells were also inhibited by the 5-HT1A-receptor agonist 8-hydroxy-2(di-n-propylamino)tetralin (8-OH-DPAT; 1-10 microM; n = 7). The data indicate that SFO neurons are responsive to serotonin via postsynaptic activation of multiple receptor subtypes. The results suggest that excitatory responses to serotonin are mediated by 5-HT2A or 5-HT2C receptors and that inhibitory responses may be mediated by 5-HT1A receptors. In addition, similar percentages of serotonin-excited and -inhibited cells were also sensitive to ANG II. As such the functional relationship between serotonin and ANG II in the SFO remains unclear.

Non-NASA Center↗

Effects of starvation on physiological activity and chlorine disinfection resistance in Escherichia coli O157:H7

Escherichia coli O157:H7 can persist for days to weeks in microcosms simulating natural conditions. In this study, we used a suite of fluorescent, in situ stains and probes to assess the influence of starvation on physiological activity based on membrane potential (rhodamine 123 assay), membrane integrity (LIVE/DEAD BacLight kit), respiratory activity (5-cyano-2,3-di-4-tolyl-tetrazolium chloride assay), intracellular esterase activity (ScanRDI assay), and 16S rRNA content. Growth-dependent assays were also used to assess substrate responsiveness (direct viable count [DVC] assay), ATP activity (MicroStar assay), and culturability (R2A agar assay). In addition, resistance to chlorine disinfection was assessed. After 14 days of starvation, the DVC values decreased, while the values in all other assays remained relatively constant and equivalent to each other. Chlorine resistance progressively increased through the starvation period. After 29 days of starvation, there was no significant difference in chlorine resistance between control cultures that had not been exposed to the disinfectant and cultures that had been exposed. This study demonstrates that E. coli O157:H7 adapts to starvation conditions by developing a chlorine resistance phenotype.

NASA Discipline Environmental Health↗

Calcium-independent activation of extracellular signal-regulated kinases 1 and 2 by cyclic strain

We have previously demonstrated that cyclic strain induces extracellular signal-regulated kinases 1 and 2 (ERK1/2) activation in endothelial cells (EC). The aim of this study was to investigate the effect of Ca2+ on the activation of ERK1/2. Bovine aortic EC were pretreated with a chelator of extracellular Ca2+, ethylaneglycol-bis(aminoethylether)-tetra-acetate (EGTA), a depleter of Ca2+ pools, 2,5-Di-(tert-butyl)-1,4-benzohydroquinone (BHQ), or a Ca2+ channel blocker, GdCl3, and subjected to an average 10 % strain at a rate of 60 cycles/min for 10 min. BHQ and GdCl3 did not inhibit the strain-induced ERK1/2 activation. Chelation of normal extracellular Ca2+ (1.8 mM) medium with EGTA (3 mM) acutely stimulated baseline phosphorylation and activation of ERK1/2, thereby obscuring any strain-induced activation of ERK1/2. However, in EC preincubated for 24 hours in Ca2+-free medium, elevated baseline phosphorylation was minimally activated by EGTA (200 microM) such that cyclic strain stimulated ERK1/2 in the presence or absence of BHQ. These results suggest a Ca2+ independence of the ERK1/2 signaling pathway by cyclic strain. Copyright 1998 Academic Press.

NASA Discipline Cell Biology↗

A reevaluation of the vestibulo-ocular reflex: new ideas of its purpose, properties, neural substrate, and disorders

Conventional views of the vestibulo-ocular reflex (VOR) have emphasized testing with caloric stimuli and by passively rotating patients at low frequencies in a chair. The properties of the VOR tested under these conditions differ from the performance of this reflex during the natural function for which it evolved--locomotion. Only the VOR (and not visually mediated eye movements) can cope with the high-frequency angular and linear perturbations of the head that occur during locomotion; this is achieved by generating eye movements at short latency (< 16 msec). Interpretation of vestibular testing is enhanced by the realization that, although the di- and trisynaptic components of the VOR are essential for this short-latency response, the overall accuracy and plasticity of the VOR depend upon a distributed, parallel network of neurons involving the vestibular nuclei. Neurons in this network variously upon a distributed, parallel network of neurons involving the vestibular nuclei. Neurons in this network variously encode inputs from the labyrinthine semicircular canals and otoliths, as well as from the visual and somatosensory systems. The central vestibular pathways branch to contact vestibular cortex (for perception) and the spinal cord (for control of posture). Thus, the vestibular nuclei basically coordinate the stabilization of gaze and posture, and contribute to the perception of verticality and self-motion. Consequently, brainstem disorders that disrupt the VOR cause not just only nystagmus, but also instability of posture (eg, increased fore-aft sway in patients with downbeat nystagmus) and disturbance of spatial orientation (eg, tilt of the subjective visual vertical in Wallenberg's syndrome).

Review↗

Review of the biological effects of weightlessness on the human endocrine system

Studies from space flights over the past two decades have demonstrated that there are basic physiological changes in humans during space flight. These changes include cephalad fluid shifts, loss of fluid and electrolytes, loss of muscle mass, space motion sickness, anemia, reduced immune response, and loss of calcium and mineralized bone. The cause of most of these manifestations is not known but the general approach has been to investigate systemic and hormonal changes. However, data from the 1973-1974 Skylabs, Spacelab 3 (SL-3), Spacelab D-I (SL-DI), and now the new SLS-1 missions support a more basic biological response to microgravity that may occur at the tissue, cellular, and molecular level. This report summarizes ground-based and SLS-1 experiments that examined the mechanism of loss of red blood cell mass in humans, the loss of bone mass and lowered osteoblast growth under space flight conditions, and loss of immune function in microgravity.

STS-40 Shuttle Project↗

Crosslinking Amine-Modified Silica Aerogels with Epoxies: Mechanically Strong Lightweight Porous Materials

The mesoporous surfaces of TMOS-derived silica aerogels have been modified with amines by co-polymerization of TMOS with APTES. The amine sites have become anchors for crosslinking the nanoparticles of the skeletal backbone of the aerogel by attachment of di-, tri and tetra-functional epoxies. The resulting conformal coatings increase the density of the native aerogels by a factor of 2-3 but the strength of the resulting materials may increase by more than two orders of magnitude. Processing variables such as amount of APTES used to make the gels, the epoxy type and concentration used for crosslinking, as well as the crosslinking temperature and time were varied according to a multivariable design-of-experiments (DOE) model. It was found that while elastic modulus follows a similar trend with density, maximum strength is attained neither at the maximum density nor at the highest concentration of -NH2 groups, suggesting surface saturation effects. Aerogels crosslinked with the tri-functional epoxide always show improved strength compared with aerogels crosslinked with the other two epoxides under identical conditions. Solid C-13 NMR studies show residual unreacted epoxides, which condense with ne another by heating crosslinked aerogels at 150 C.

Meador, Mary Ann B.↗

The Mars Exploration Rover Cameras: A Status Report

With more than 68,000 images returned from the surface of Mars to date, the Mars Exploration Rover (MER) camera suite continues to perform extremely well. Image signal to noise ratios (SNRs) are greater than 200:1, flat fields remain stable, and single-pixel degradation has been negligible. Acting as the eyes of the robotic field geologists, the 18 MER cameras continue to play a leading role in major scientific findings at both Gusez Crater and Meridiana Planum. All 4 types of cameras, the hazard avoidance (Hazcam), navigation (Navcam), the color panoramic (Pancam) and the microscopic imager (MI), continue to return data from the Martian surface from both Rovers. In addition to the rover cameras, each lander utilized a descent imager (DI) to help facilitate safe landing and provide landing site context. The Pancam and MI are part of the scientific instrument payload of the rovers. In addition to gathering gathering science image data, the Pacams also support sun finding and measure atmospheric dust optical depth. The Hazcam and Navcam stereo pairs are used for traverse planning, autonomous navigation and general imaging.

Schwochert, M. A.↗

Lightning Mapping and the Nowcasting of Severe Storms

This paper describes a successful research and operational collaboration between NASA scientists and NWS forecasters to improve severe stor m warnings using real-time data from a regional VHF total lightning mapping array (LMA). Key objectives of our research using LMA data ar e: a) Identification of intensifying and weakening storms using the time rate-of-change of total flash rate; b) Improved severe storm poten tial situational awareness; c) Evaluation of the potential of total f lash rate trend to improve severe storm probability of detection (POD ) and lead time; and d) Validation of mesoscale model forecasts of th understorm initiation. The LMA data are distributed for ingest and di splay in the WFO AWIPS decision support system, and archived at each WFO for case studies, event playbacks, and assessments using the NWS Warning Event Simulator. The Huntsville WFO has upgraded severe thund erstorm warnings to verified tornado warnings and avoided a false ala rm on a severe storm through the added information on storm growth, intensification, and decay that can be deduced from the magnitude and temporal trend of total flash rates. We present detailed case studies of the observed relationships between lightning activity and tornadi c storm development as determined by radar reflectivity and velocity fields, and thunderstorms forecast by the Weather Research and Foreca st (WRF) model. From these collaborative studies, forecasters can eva luate the added value of total lightning data within the forecast and warning decision-making process (http://weather.msfc.nasa.gov/sport) .

Goodman, S.↗

Dissolution kinetics of iron-, manganese-, and copper-containing synthetic hydroxyapatites

Micronutrient-substituted synthetic hydroxyapatite (SHA) is being evaluated by the National Aeronautics and Space Administration's (NASA) Advanced Life Support (ALS) Program for crop production on long-duration human missions to the International Space Station or for future Lunar or Martian outposts. The stirred-flow technique was utilized to characterize Ca, P, Fe, Mn, and Cu release characteristics from Fe-, Mn-, and Cu-containing SHA in deionized (DI) water, citric acid, and diethylene-triamine-pentaacetic acid (DTPA). Initially, Ca and P release rates decreased rapidly with time and were controlled by a non-SHA calcium phosphate phase(s) with low Ca/P solution molar ratios (0.91-1.51) relative to solid SHA ratios (1.56-1.64). At later times, Ca/P solution molar ratios (1.47-1.79) were near solid SHA ratios and release rates decreased slowly indicating that SHA controlled Ca and P release. Substituted SHA materials had faster dissolution rates relative to unsubstituted SHA. The initial metal release rate order was Mn >> Cu > Fe which followed metal-oxide/phosphate solubility suggesting that poorly crystalline metal-oxides/phosphates were dominating metal release. Similar metal release rates for all substituted SHA (approximately 0.01 cmol kg-1 min-1) at the end of the DTPA experiment indicated that SHA dissolution was supplying the metals into solution and that poorly crystalline metal-oxide/phosphates were not controlling metal release. Results indicate that non-SHA Ca-phosphate phases and poorly crystalline metal-oxide/phosphates will contribute Ca, P, and metals. After these phases have dissolved, substituted SHA will be the source of Ca, P, and metals for plants.

NASA Discipline Life Support Systems↗

Numerical Evaluation of P-Multigrid Method for the Solution of Discontinuous Galerkin Discretizations of Diffusive Equations

This paper describes numerical experiments with P-multigrid to corroborate analysis, validate the present implementation, and to examine issues that arise in the implementations of the various combinations of relaxation schemes, discretizations and P-multigrid methods. The two approaches to implement P-multigrid presented here are equivalent for most high-order discretization methods such as spectral element, SUPG, and discontinuous Galerkin applied to advection; however it is discovered that the approach that mimics the common geometric multigrid implementation is less robust, and frequently unstable when applied to discontinuous Galerkin discretizations of di usion. Gauss-Seidel relaxation converges 40% faster than block Jacobi, as predicted by analysis; however, the implementation of Gauss-Seidel is considerably more expensive that one would expect because gradients in most neighboring elements must be updated. A compromise quasi Gauss-Seidel relaxation method that evaluates the gradient in each element twice per iteration converges at rates similar to those predicted for true Gauss-Seidel.

Atkins, H. L.↗

Evaluation of Airborne Precision Spacing in a Human-in-the-Loop Experiment

A significant bottleneck in the current air traffic system occurs at the runway. Expanding airports and adding new runways will help solve this problem; however, this comes with significant costs: financially, politically and environmentally. A complementary solution is to safely increase the capacity of current runways. This can be achieved by precisely spacing aircraft at the runway threshold, with a resulting reduction in the spacing bu er required under today s operations. At NASA's Langley Research Center, the Airspace Systems program has been investigating airborne technologies and procedures that will assist the flight crew in achieving precise spacing behind another aircraft. A new spacing clearance allows the pilot to follow speed cues from a new on-board guidance system called Airborne Merging and Spacing for Terminal Arrivals (AMSTAR). AMSTAR receives Automatic Dependent Surveillance-Broadcast (ADS-B) reports from an assigned, leading aircraft and calculates the appropriate speed for the ownship to fly to achieve the desired spacing interval, time- or distance-based, at the runway threshold. Since the goal is overall system capacity, the speed guidance algorithm is designed to provide system-wide benefits and stability to a string of arriving aircraft. An experiment was recently performed at the NASA Langley Air Traffic Operations Laboratory (ATOL) to test the flexibility of Airborne Precision Spacing operations under a variety of operational conditions. These included several types of merge and approach geometries along with the complementary merging and in-trail operations. Twelve airline pilots and four controllers participated in this simulation. Performance and questionnaire data were collected from a total of eighty-four individual arrivals. The pilots were able to achieve precise spacing with a mean error of 0.5 seconds and a standard deviation of 4.7 seconds. No statistically significant di erences in spacing performance were found between in-trail and merging operations or among the three modeled airspaces. Questionnaire data showed general acceptance for both pilots and controllers. These results reinforce previous findings from full-mission simulation and flight evaluation of the in-trail operations. This paper reviews the results of this simulation in detail.

Barmore, Bryan E.↗