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NASA NTRS2002

Transcriptional control of monolignol biosynthesis in Pinus taeda: factors affecting monolignol ratios and carbon allocation in phenylpropanoid metabolism

Transcriptional profiling of the phenylpropanoid pathway in Pinus taeda cell suspension cultures was carried out using quantitative real time PCR analyses of all known genes involved in the biosynthesis of the two monolignols, p-coumaryl and coniferyl alcohols (lignin/lignan precursors). When the cells were transferred to a medium containing 8% sucrose and 20 mm potassium iodide, the monolignol/phenylpropanoid pathway was induced, and transcript levels for phenylalanine ammonia lyase, cinnamate 4-hydroxylase, p-coumarate 3-hydroxylase, 4-coumarate:CoA ligase, caffeoyl-CoA O-methyltransferase, cinnamoyl-CoA reductase, and cinnamyl alcohol dehydrogenase were coordinately up-regulated. Provision of increasing levels of exogenously supplied Phe to saturating levels (40 mm) to the induction medium resulted in further up-regulation of their transcript levels in the P. taeda cell cultures; this in turn was accompanied by considerable increases in both p-coumaryl and coniferyl alcohol formation and excretion. By contrast, transcript levels for both cinnamate 4-hydroxylase and p-coumarate 3-hydroxylase were only slightly up-regulated. These data, when considered together with metabolic profiling results and genetic manipulation of various plant species, reveal that carbon allocation to the pathway and its differential distribution into the two monolignols is controlled by Phe supply and differential modulation of cinnamate 4-hydroxylase and p-coumarate 3-hydroxylase activities, respectively. The coordinated up-regulation of phenylalanine ammonia lyase, 4-coumarate:CoA ligase, caffeoyl-CoA O-methyltransferase, cinnamoyl-CoA reductase and cinnamyl alcohol dehydrogenase in the presence of increasing concentrations of Phe also indicates that these steps are not truly rate-limiting, because they are modulated according to metabolic demand. Finally, the transcript profile of a putative acid/ester O-methyltransferase, proposed as an alternative catalyst for O-methylation leading to coniferyl alcohol, was not up-regulated under any of the conditions employed, suggesting that it is not, in fact, involved in monolignol biosynthesis.

NASA Discipline Plant Biology↗

NASA NTRS1989

An isotopic study of biogeochemical relationships between carbonates and organic carbon in the Greenhorn Formation

Carbon-isotopic compositions of total carbonate, inoceramid carbonate, micritic carbonate, secondary cements, total organic carbon, and geoporphyrins have been measured in 76 different beds within a 17-m interval of a core through the Greenhorn Formation, an interbedded limestone and calcareous shale unit of Cretaceous age from the Western Interior Seaway of North America. Results are considered in terms of variations in the processes of primary production and in secondary processes. It is shown that the porphyrin isotopic record reflects primary isotopic variations more closely than the TOC isotopic record and that, in these sediments, TOC is enriched in C-13 relative to its primary precursor by 0.6 to 2.8 percent. This enrichment is attributed to isotope effects within the consumer foodweb and is associated with respiratory heterotrophy. Variation in this secondary enrichment are correlated with variations in the isotopic composition of marine carbonate.

Hayes, J. M.↗

NASA NTRS2011

Fracture in Phenolic Impregnated Carbon Ablator

The thermal protection materials used for spacecraft heat shields are subjected to various thermal-mechanical loads during an atmospheric entry which can threaten the structural integrity of the system. This paper discusses the development of a novel technique to understand the failure mechanisms inside thermal protection materials. The focus of research is Phenolic Impregnated Carbon Ablator (PICA). It has successfully flown on the Stardust spacecraft and is the TPS material chosen for the Mars Science Laboratory (MSL) and Dragon spacecraft. Although PICA has good thermal properties, structurally, it is a weak material. In order to thoroughly understand failure in PICA, fracture tests were performed on FiberForm* (precursor of PICA), virgin and charred PICA materials. Several samples of these materials were tested to investigate failure mechanisms at a microstructural scale. Stress-strain data were obtained simultaneously to estimate the fracture toughness. It was found that cracks initiated and grew in the FiberForm when a critical stress limit was reached such that the carbon fibers separated from the binder. However, both for virgin and charred PICA, crack initiation and growth occurred in the matrix (phenolic) phase. Both virgin and charred PICA showed greater strength values compared to FiberForm coupons, confirming that the presence of the porous matrix helps in absorbing the fracture energy.

Agrawal, Parul↗

NASA NTRS2001

Secondary metabolism in simulated microgravity

We have studied microbial secondary metabolism in a simulated microgravity (SMG) environment provided by NASA rotating-wall bioreactors (RWBs). These reactors were designed to simulate some aspects of actual microgravity that occur in space. Growth and product formation were observed in SMG in all cases studied, i.e., Bacillus brevis produced gramicidin S (GS), Streptomyces clavuligerus made beta-lactam antibiotics, Streptomyces hygroscopicus produced rapamycin, and Escherichia coli produced microcin B17 (MccB17). Of these processes, only GS production was unaffected by SMG; production of the other three products was inhibited. This was determined by comparison with performance in an RWB positioned in a different mode to provide a normal gravity (NG) environment. Carbon source repression by glycerol of the GS process, as observed in shaken flasks, was not observed in the RWBs, whether operated in the SMG or NG mode. The same phenomenon occurred in the case of MccB17 production, with respect to glucose repression. Thus, the negative effects of carbon source on GS and beta-lactam formation are presumably dependent on shear, turbulence, and/or vessel geometry, but not on gravity. Stimulatory effects of phosphate and the precursor L-lysine on beta-lactam antibiotic production, as observed in flasks, also occurred in SMG. An almost complete shift in the localization of produced MccB17 from cells to extracellular medium was observed when E. coli was grown in the RWB under SMG or NG. If a plastic bead was placed in the RWB, accumulation became cellular, as it is in shaken flasks, indicating that sheer stress favors a cellular location. In the case of rapamycin, the same type of shift was observed, but it was less dramatic, i.e., growth in the RWB under SMG shifted the distribution of produced rapamycin from 2/3 cellular:1/3 extracellular to 1/3 cellular:2/3 extracellular. Stress has been shown to induce or promote secondary metabolism in a number of other microbial systems. RWBs provide a low stress SMG environment, which, however, supports only poor production of MccB17, as compared to production in shaken flasks. We wondered whether the poor production in RWBs under SMG is due to the low level of stress, and whether increasing stress in the RWBs would raise the amount of MccB17 formed. We found that increasing shear stress by adding a single Teflon bead to the RWB improved MccB17 production. Although shear stress seems to have a marked positive effect on MccB17 production in SMG, addition of various concentrations of ethanol to RWBs (or to shaken flasks) failed to increase MccB17 production. Ethanol stress merely decreased production and, at higher concentrations, inhibited growth. Interestingly, cells growing in the RWB were much more resistant to the growth- and production-inhibitory effects of ethanol than cells growing in shaken flasks. With respect to S. hygroscopicus, addition of Teflon beads to the RWB reversed the inhibition of growth, but rapamycin production was still markedly inhibited, and the distribution did not revert back to a preferential cellular site.

NASA Discipline Cell Biology↗

NASA NTRS2012

Compound-Specific Carbon, Nitrogen, and Hydrogen Isotopic Ratios for Amino Acids in CM and CR Chondrites and their use in Evaluating Potential Formation Pathways

Stable hydrogen, carbon, and nitrogen isotopic ratios (oD, 013C, and olSN) of organic compounds can revcal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1I2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CRZ Graves Nunataks (GRA) 95229, CRZ Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing ODC and increasing oD with increasing carbon number in the aH, (l-NH2 amino acids that correspond to predictions made for formation via Streckercyanohydrin synthesis. We also observe light ODC signatures for ~-alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ro-amino acids). Higher deuterium enrichments are observed in amethyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than CM chondrites, reflecting different parent-body chemistry.

Elsila, Jamie E.↗

NASA NTRSDate not supplied

In-Situ Reaction Monitoring for Lunar Applications Utilizing a Single Quadrupole Residual Gas Analyzer

With a revived focus to create a permanent presence on the moon and in preparation for future Mars exploration, it is imperative that all resources are utilized to their fullest potential.[1] In-Situ Resource Utilization (ISRU) will be critical for future mission success as it would enable independent operation of missions while minimally relying on the complex supply chain created between the Earth, moon and Mars. One of the most critical resources that have been identified for ISRU is the creation of liquid oxygen(LO2) for not only breathable air, but also for rocket propellant. On the moon and potentially Mars, one of the most O2 rich resources is in the presence of regolith.[2],[3] Although there are numerous minerals within regolith and various processes to extract O2,this is not the scope of this paper. Since the O2 extraction method can vary, a critical standardized analytical method is needed to verify O2(or oxygenated precursor compounds) for extraction efficiency and purity. Our group utilizes a modified consumer off-the-shelf (COTS), Residual Gas Analyzer (RGA) Single Quadrupole Mass Spectrometer (QMS). Due to the current field mission requirements, the gas analysis module will need to rely only on mass-to-charge ratios (m/z) and peak intensities to differentiate and quantitate targeted gas-phase reactants or products, i.e. carbon monoxide(CO), carbon dioxide (CO2), methane (CH4) and hydrogen (H2). However, due to solar wind implanted volatiles and various other compounds present in lunar regolith, such as nitrogen (N2), helium (He), and deuterium (D2), deconvolution and quantification of isobaric compounds becomes quite difficult. Specifically, the presence of N2 makes quantification of CO, an oxygenated precursor, difficult due to both compounds having a peak at m/z 28.

Mass Spectrometry↗

NASA NTRS1996

Nitrogen metabolism in Lignifying Pinus taeda cell cultures

The primary metabolic fate of phyenylalanine, following its deamination in plants, is conscription of its carbon skeleton for lignin, suberin, flavonoid, and related metabolite formation. Since this accounts for approximately 30-40% of all organic carbon, an effective means of recycling the liberated ammonium ion must be operative. In order to establish how this occurs, the uptake and metabolism of various 15N-labeled precursors (15N-Phe, 15NH4Cl, 15N-Gln, and 15N-Glu) in lignifying Pinus taeda cell cultures was investigated, using a combination of high performance liquid chromatography, 15N NMR, and gas chromatograph-mass spectrometry analyses. It was found that the ammonium ion released during active phenylpropanoid metabolism was not made available for general amino acid/protein synthesis. Rather it was rapidly recycled back to regenerate phenylalanine, thereby providing an effective means of maintaining active phenylpropanoid metabolism with no additional nitrogen requirement. These results strongly suggest that, in lignifying cells, ammonium ion reassimilation is tightly compartmentalized.

NASA Discipline Number 40-50↗

NASA NTRS2007

Future Climate Impacts of Direct Radiative Forcing Anthropogenic Aerosols, Tropospheric Ozone, and Long-lived Greenhouse Gases

Long-lived greenhouse gases (GHGs) are the most important driver of climate change over the next century. Aerosols and tropospheric ozone (O3) are expected to induce significant perturbations to the GHG-forced climate. To distinguish the equilibrium climate responses to changes in direct radiative forcing of anthropogenic aerosols, tropospheric ozone, and GHG between present day and year 2100, four 80-year equilibrium climates are simulated using a unified tropospheric chemistry-aerosol model within the Goddard Institute for Space Studies (GISS) general circulation model (GCM) 110. Concentrations of sulfate, nitrate, primary organic (POA) carbon, secondary organic (SOA) carbon, black carbon (BC) aerosols, and tropospheric ozone for present day and year 2100 are obtained a priori by coupled chemistry-aerosol GCM simulations, with emissions of aerosols, ozone, and precursors based on the Intergovernmental Panel on Climate Change (IPCC) Special Report on Emissions Scenario (SRES) A2. Changing anthropogenic aerosols, tropospheric ozone, and GHG from present day to year 2100 is predicted to perturb the global annual mean radiative forcing by +0.18 (considering aerosol direct effects only), +0.65, and +6.54 W m(sup -2) at the tropopause, and to induce an equilibrium global annual mean surface temperature change of +0.14, +0.32, and +5.31 K, respectively, with the largest temperature response occurring at northern high latitudes. Anthropogenic aerosols, through their direct effect, are predicted to alter the Hadley circulation owing to an increasing interhemispheric temperature gradient, leading to changes in tropical precipitation. When changes in both aerosols and tropospheric ozone are considered, the predicted patterns of change in global circulation and the hydrological cycle are similar to those induced by aerosols alone. GHG-induced climate changes, such as amplified warming over high latitudes, weakened Hadley circulation, and increasing precipitation over the Tropics and high latitudes, are consistent with predictions of a number of previous GCM studies. Finally, direct radiative forcing of anthropogenic aerosols is predicted to induce strong regional cooling over East and South Asia. Wintertime rainfall over southeastern China and the Indian subcontinent is predicted to decrease because of the increased atmospheric stability and decreased surface evaporation, while the geographic distribution of precipitation is also predicted to be altered as a result of aerosol-induced changes in wind flow.

Chen, Wei-Ting↗

NASA NTRS2005

Development of Carbon-Nanotube/Polymer Composites

A report presents a short discussion of one company's effort to develop composites of carbon nanotubes in epoxy and other polymer matrices. The focus of the discussion is on the desirability of chemically modifying carbon nanotubes to overcome their inherent chemical nonreactivity and thereby enable the formation of strong chemical bonds between nanotubes and epoxies (or other polymeric matrix materials or their monomeric precursors). The chemical modification is effected in a process in which discrete functional groups are covalently attached to the nanotube surfaces. The functionalization process was proposed by the company and demonstrated in practice for the first time during this development effort. The covalently attached functional groups are capable of reacting with the epoxy or other matrix resin to form covalent bonds. Furthermore, the company uses this process to chemically modify the nanotube surfaces, affording tunable adhesion to polymers and solubility in select solvents. Flat-sheet composites containing functionalized nanotubes demonstrate significantly improved mechanical, thermal, and electrical properties.

Reynolds, Thomas A.↗

NASA NTRS1989

Process for coating an object with silicon carbide

A process for coating a carbon or graphite object with silicon carbide by contacting it with silicon liquid and vapor over various lengths of contact time. In the process, a stream of silicon-containing precursor material in gaseous phase below the decomposition temperature of said gas and a co-reactant, carrier or diluent gas such as hydrogen is passed through a hole within a high emissivity, thin, insulating septum into a reaction chamber above the melting point of silicon. The thin septum has one face below the decomposition temperature of the gas and an opposite face exposed to the reaction chamber. The precursor gas is decomposed directly to silicon in the reaction chamber. A stream of any decomposition gas and any unreacted precursor gas from said reaction chamber is removed. The object within the reaction chamber is then contacted with silicon, and recovered after it has been coated with silicon carbide.

Levin, Harry↗

NASA NTRS2019

A Novel Organic-Rich Meteoritic Clast from the Outer Solar System

The Zag meteorite which is a thermally-metamorphosed H ordinary chondrite contains a primitive xenolithic clast that was accreted to the parent asteroid after metamorphism. The cm-sized clast contains abundant large organic grains or aggregates up to 20 μm in phyllosilicate-rich matrix. Here we report organic and isotope analyses of a large (~10 μm) OM aggregate in the Zag clast. The X-ray micro-spectroscopic technique revealed that the OM aggregate has sp2 dominated hydrocarbon networks with a lower abundance of heteroatoms than in IOM from primitive (CI,CM,CR) carbonaceous chondrites, and thus it is distinguished from most of the OM in carbonaceous meteorites. The OM aggregate has high D/H and (sup 15)N/(sup 14)N ratios (δD = 2,370 ± 74‰ and δ(sup 15)N = 696 ± 100‰), suggesting that it originated in a very cold environment such as the interstellar medium or outer region of the solar nebula, while the OM is embedded in carbonate-bearing matrix resulting from aqueous activities. Thus, the high D/H ratio must have been preserved during the extensive late-stage aqueous processing. It indicates that both the OM precursors and the water had high D/H ratios. Combined with (sup 16)O-poor nature of the clast, the OM aggregate and the clast are unique among known chondrite groups. We further propose that the clast possibly originated from D/P type asteroids or trans-Neptunian Objects.

Yoko Kebukawa↗

NASA NTRS2000

Global Warming in the 21st Century: An Alternate Scenario

A common view is that the current global warming rate will continue or accelerate. But we argue that rapid warming in recent decades has been driven by non-CO2 greenhouse gases (GHGs), such as CFCs, CH4 and N2O, not by the products of fossil fuel burning, CO2 and aerosols, whose positive and negative climate forcings are partially offsetting. The growth rate of non-CO2 GHGs has declined in the past decade. If sources of CH4 and O3 precursors were reduced in the future, the change of climate forcing by non-CO2 GHGs In the next 50 years could be near zero. Combined with a reduction of black carbon emissions and plausible success in slowing CO2 emissions, this could lead to a decline in the rate of global warming, reducing the danger of dramatic climate change. Such a focus on air pollution has practical benefits that unite the interests of developed and developing countries. However, assessment of ongoing and future climate change requires composition-specific longterm global monitoring of aerosol properties.

Hansen, James E.↗

NASA NTRS2000

Global Warming in the Twenty-First Century: An Alternative Scenario

A common view is that the current global warming rate will continue or accelerate. But we argue that rapid warming in recent decades has been driven mainly by non-CO2 greenhouse gases (GHGs), such as chlorofluorocarbons, CH4, and N2O, not by the products of fossil fuel burning, CO2 and aerosols, the positive and negative climate forcings of which are partially offsetting. The growth rate of non-CO2 GHGs has declined in the past decade. If sources of CH4 and O3 precursors were reduced in the future, the change in climate forcing by non-CO2 GHGs in the next 50 years could be near zero. Combined with a reduction of black carbon emissions and plausible success in slowing CO2 emissions, this reduction of non-CO2 GHGs could lead to a decline in the rate of global warming, reducing the danger of dramatic climate change. Such a focus on air pollution has practical benefits that unite the interests of developed and developing countries. However, assessment of ongoing and future climate change requires composition specific long-term global monitoring of aerosol properties.

Hansen, James↗

NASA NTRS2000

Global Warming in the Twenty-First Century: An Alternative Scenario

Hansen, James↗

NASA NTRS1982

The prebiological paleoatmosphere - Stability and composition

In the past, it was generally assumed that the early atmosphere of the earth contained appreciable quantities of methane (CH4) and ammonia (NH3). This was the type of atmosphere believed to be the most suitable environment for chemical evolution, the nonbiological formation of complex organic molecules, the precursors of living systems. Photochemical considerations suggest that a CH4-NH3 dominated early atmosphere was probably very short-lived, if it ever existed at all. Instead, an early atmosphere of carbon dioxide (CO2) and nitrogen (N2) is favored by photochemical as well as geological and geochemical considerations. Photochemical calculations also indicate that the total oxygen column density of the prebiological paleoatmosphere did not exceed 10 to the -7th of the present atmospheric level.

Levine, J. S.↗

NASA NTRS2001

Polyimide Composites from 'Salt-Like' Solution Precursors

Four NASA Langley-developed polyimide matrix resins, LaRC(TM)-IA, LaRC(TM)-IAX, LaRC(TM)-8515 and LaRC(TM)-PETI-5, were produced via a 'saltlike' process developed by Unitika Ltd. The salt-like solutions (65% solids in NMP) were prepregged onto Hexcel IM7 carbon fiber using the NASA LaRC multipurpose tape machine. Process parameters were determined and composite panels fabricated. The temperature dependent volatile depletion rates, the thermal crystallization behavior and the resin rheology were characterized. Composite molding cycles were developed which consistently yielded well consolidated, void-free laminated parts. Composite mechanical properties such as the short beam shear strength; the longitudinal and transverse flexural strength and flexural modulus; the longitudinal compression strength and modulus; and the open hole compression strength and compression after impact strength were measured at room temperature and elevated temperatures. The processing characteristics and the composite mechanical properties of the four intermediate modulus carbon fiber/polyimide matrix composites were compared to existing data on the same polyimide resin systems and IM7 carbon fiber manufactured via poly(amide acid) solutions (30-35% solids in NMP). This work studies the effects of varying the synthetic route on the processing and mechanical properties of the polyimide composites.

Cano, Roberto J.↗

NASA NTRS1999

Oxygen Generator System Mars In-Situ Propellant Production Precursor Flight

The 2001 Lander to Mars will carry the first ever ISRU payload to Mars. This payload, the Mars In-situ Propellant production Precursor (MIP), will demonstrate a variety of technologies that will be required for future ISRU Mars indigenous material processing plant designs. One of those technologies is that of extracting oxygen from the predominantly carbon dioxide atmosphere of Mars, a prerequisite for future sample return and human missions to Mars. The Oxygen Generator Subsystem (OGS) portion of the MIP will demonstrate this and is the focus of this paper. The primary objective of the OGS is to demonstrate the production of oxygen from Mars atmospheric gases. Secondary objectives are to measure the performance and reliability of oxygen generation hardware in actual mission environments over an extended time. Major constraints on the OGS design came from several sources. The Lander provides power to the system from solar power that is harnessed by photovoltaic arrays. This limited OGS to daytime only operations (six to eight hours) and a maximum power of 15W. The reliance on solar power necessitated thermal cycling of the OGS between Mars ambient and OGS operating temperatures. The Lander also limited the total mass of the MIP payload to 7.5 kg with a correspondingly small volume, and the OGS was one of six experiments in the MIP. Mass and volume were to be minimized. Another constraint was cost. Mission funding, as always, was tight. Cost was to be minimized. In short the OGS design had to be low power (<15 Watts), low mass (1 kg), low volume, low cost, and be capable of cyclical operations for an extended stay on Mars. After extensive research, a zirconia based solid oxide electrolyzer design was selected.

Sridhar, K. R.↗

NASA NTRS1999

Oxygen Generator System Mars In-Situ Propellant Production Precursor Flight

The 2001 Lander to Mars will carry the first ever In situ Resource Utilization (ISRU) payload to Mars. This payload, the Mars In-situ Propellant production Precursor (MIP), will demonstrate a variety of technologies that will be required for future ISRU Mars indigenous material processing plant designs. One of those technologies is that of extracting oxygen from the predominantly carbon dioxide atmosphere of Mars, a prerequisite for future sample return and human missions to Mars. The Oxygen Generator Subsystem (OGS) portion of the MIP will demonstrate this and is the focus of this paper. The primary objective of the OGS is to demonstrate the production of oxygen from Mars atmospheric gases. Secondary objectives are to measure the performance and reliability of oxygen generation hardware in actual mission environments over an extended time. Major constraints on the OGS design came from several sources. The Lander provides power to the system from solar power that is harnessed by photovoltaic arrays. This limited OGS to daytime only operations (six to eight hours) and a maximum power of 15W. The reliance on solar power necessitated thermal cycling of the OGS between Mars ambient and OGS operating temperatures. The Lander also limited the total mass of the MIP payload to 7.5 kg with a correspondingly small volume, and the OGS was one of six experiments in the MIP Mass and volume were to be minimized. Another constraint was cost. Mission funding, as always, was tight. Cost was to be minimized. In short the OGS design had to be low power (<15 Watts), low mass (1 kg), low volume, low cost, and be capable of cyclical operations for an extended stay on Mars. After extensive research, a zirconia based solid oxide electrolyzer design was selected.

Sridhar, K. R.↗