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All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Influence of Hyperfine Coupling Strain on Two-Dimensional ESEEM Spectra from I = 1/2 Nuclei

HYSCORE, a variant of two-dimensional ESEEM spectroscopy, is currently one of the most effective tools in high-resolution solid-state EPR spectroscopy. Our systematic studies of hydrogen bonds with semiquinones in 15 N-labeled proteins have previously provided us with an extensive collection of 15 N HYSCORE spectra produced by N–H…O nitrogen donors. Examination of these spectra has indicated in several cases lineshape distortions not described by available theoretical models. We were able to explain all observed artificial phenomena in the 15 N spectra of semiquinones considering a single mechanism—strain of the isotropic hyperfine interaction. In this review article, we introduce the HYSCORE experiment and the theoretical background for spectra of I = 1/2 nuclei in orientation-disordered samples. We then present a description of the observed lineshape distortions and an explanation of the hyperfine strain’s influence on the experimental spectra. In the final part of the article, we discuss (i) similar lineshape distortions found in previously published spectra from 15 N, 29 Si, 31 P, and 57 Fe nuclei that can be explained using the approach applied for the analysis of the 15 N spectra of semiquinones, and (ii) a recently published analysis of 31P spectra with a different type of lineshape distortion based on a more sophisticated method, where the strength of anisotropic coupling is correlated with the sign and value of the isotropic constant in different conformations of a Cu(II) complex.

30 DIRECT ENERGY CONVERSION↗
NASA NTRS1997

Observations and Modeling of the Transient General Circulation of the North Pacific Basin

The objective of this study was to clarify the role that interstellar-cloud chemistry played in forming the population of organic molecules presently found in carbonaceous meteorites. This goal was to be achieved by means of defining the isotopic components present in organic and related phases in the meteorites and thereby identify the processes and source reservoirs involved in organic synthesis in the early solar system. Isotopic analysis of separated amino acids from the Murchison meteorite yielded results that are complex and not fully interpretable at this time. Substantial inter-acid variability in D/H ratio was observed, some but not all of which could be attributed to exchange with terrestrial hydrogen. Pronounced, though smaller, variability was also found for N-15/N-14 ratios. For both D/H and N-15/N-14 data, observed meteoritic values were substantially greater than found in terrestrial materials, providing a robust constraint on degrees of possible terrestrial contamination. Also, C-13/C-12 ratios, though falling within the range of data found on earth, significantly exceeded those characteristic of naturally occurring terrestrial amino acids. Inter-acid variability in C-13/C-12 ratios was muted relative to that observed for D/H and N-15/N-14 but still lay well outside of experimental uncertainty. No systematic relationship could be observed between variations in H, C and N isotopes. Two anomalous components were also found during the course of this study. A highly (greater than 6% relative to terrestrial) N-15-depleted, N-rich compound, which has not yet been identified, co-eluted with some amino acids. Clearly the Murchison meteorite sampled nitrogen from a number of highly diverse isotopic reservoirs. In fact, from this and related studies, it is now apparent that the distribution of nitrogen isotopes in the primitive solar system was extremely inhomogeneous. The second anomalous result obtained in the present study was for an extract of 'ammonia' from Murchison. It should be noted that this sample consisted of ammonia that was probably derived from a number of different compounds present in the meteorite itself, possibly including amines and amides, as well as ammonia sensu strictu and ammonium slats. However, the significance of this analysis is that the N-15/N-14 ratio measured was much lower than those found for the meteoritic amino acids (+2% vs around + 9% relative to terrestrial). This raises an important question concerning the source of the ammonia that was involved in synthesis of the amino acids. This issue needs to be explored further.

Kerridge, John F.↗
DOE OSTI2022

The quality of organic amendments affects soil microbiome and nitrogen-cycling bacteria in an organic farming system

Organic amendments are applied in organic farming systems to provide nutrients for crop uptake and to improve soil health. Compost is often favored over fresh manure for food safety reasons, while fresh manure can be a valuable source of readily available nitrogen (N). However, the potential for fresh versus composted manure to differentially affect soil microbial and N-cycling functional communities over multiple seasons remains unknown. We compared the effect of composted vs. fresh cattle manure on soil microbial communities using taxonomic and functional approaches. Soils were collected from field plots with three organic N treatments: control (no amendment), composted manure (compost, 224 kg/ha total N), and fresh manure (manure, 224 kg/ha total N) in an organic production system. Illumina amplicon sequencing was used to comprehensively assess the bacterial community (16S rRNA genes), fungal community (ITS), ureolytic community ( ureC ), chitinolytic community ( chiA ), bacterial ammonia oxidizers (AOB amoA ), and nitrite oxidizers ( Nitrospira nxrB ). The results showed that both compost and manure treatment significantly changed the soil microbial communities. Manure had a stronger effect than compost on soil bacterial and fungal community composition, as well as on the ureolytic and chitinolytic communities, while compost treated soils had higher microbial richness than manure treated soils. Both taxonomic and functional approaches showed that the microbial community was more responsive to fresh manure than to compost. Manure treated soil also had more complex microbial interactions than compost treated soil. The abundance and community composition of N-cycling functional groups often played more limited roles than soil chemical properties (soil organic carbon, extractable organic carbon, and pH) in driving N-cycling processes. Results from our study may guide strategies for the management of organic amendments in organic farming systems and provide insights into the linkages between soil microbial communities and soil function.

Ouyang, Yang↗
NASA NTRSDate not supplied

Interoperable Map Services with Performance Tuning for Earth Science Data through API-Tiles and Dynamic API-Styles

NASA’s Goddard Earth Sciences Data and Information Services Center (GES DISC) provides access to a wide range of global climate data from various satellite missions and models. However, the visualization and analysis of these data can be challenging due to their large volume, complex structure, and diverse formats. This study presents the implementation of interoperable map services (API-Maps) with performance tuning using API-Tiles and dynamic API-Styles. API-Maps is a standard for defining and exposing map services through RESTful (representational state transfer) APIs (application programming interfaces). API-Tiles is a technique for generating and delivering map tiles on demand from any data source. API-Styles is a method for dynamically applying styles to map tiles based on user preferences or data attributes. The use of API-Tiles and dynamic API-Styles enhances the performance and scalability of the map services, allowing for smooth and interactive visualization of large datasets. Two types of Earth Science data sources from the NASA GES DISC are used in the experiment: regularly gridded data, such as Global Precipitation Measurement (GPM) precipitation data, and low processing level data, such as low-level data of atmospheric composite measurements from the TROPOspheric Monitoring Instrument (TROPOMI) mission. Re-gridding of swath data (low level data - e.g. Level 2) of atmospheric composites (e.g. TROPOMI products, such as nitrogen dioxide, ozone and aerosol optical depth) is applied to enable the Web-based, interoperable, tiled, and styled mapping (rendering) services of such data. The results demonstrate the effectiveness of the proposed approach in providing fast and efficient access to Earth science data through interoperable map services.

Geographic Information System↗
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 permeant presence on the moon and in preparation for future Mars exploration, it is imperative that all re-sources are utilized to their fullest potential. 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 (O2) for not only breathable air, but also for rocket fuel. On the moon and potentially Mars, one of the most O2 rich resources is in the presence of regolith. 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. Approaches to differentiate isobaric components: Initially, the solution to overcome isobaric overlap was to use isotopic ratios, particularly be-tween carbon-13 and nitrogen-15. Although limited literature discuss isotopic composition and attempt to quantify the ratios, variation is particularly high and limited to a few lunar regolith samples. The following were identified as potential approaches to quantify isobaric species, N2 and CO, using our RGA. Threshold Ionization. CO and N2 both have peaks at m/z 28, but only N2 is capable of producing a peak at m/z 7. While a N2 peak at m/z 7 is generally rare, instrument parameters can be optimized in order to maximize the peak intensity. Typically a standard ionization energy of 70 eV is used to monitor a batch process and would produce reliable results for a majority of the reactants or products that we are interested in quantifying. However, to analyze the rare molecular fragment of N2 (N2+ at m/z 7), a different ionization energy may be beneficial. Threshold Ionization Mass Spectrometry (TIMS) will be explored to optimize the N2+ peak at m/z 7 by varying parameters such as ionization energy and pressure. Therefore, a quantitative value at m/z 7 will be used to determine the product gas concentration of N2, which will be subtracted from the total concentration determined at m/z 28 enabling us to approximate the amount of CO. Secondary Detector (infrared gas detector, IR). Another approach to quantitate and differentiate be-tween isobaric components is to leverage alternative modes of detection. Unlike mass spectrometry, which generally uses a separation step prior to analysis (i.e. gas chromatography), IR produces energy that is specifically absorbed depending on the bond and configuration of the molecule. This technique could be leveraged since it is generally only active on non-symmetric molecules, i.e. CO. Utilizing concentrations of CO determined from another detector could help correct concentrations of CO obtained from the QMS. However, the inclusion of another detector adds additional mission requirements, such as power, software changes and avionics updates that add additional cost and schedule requirements.

mass spectrometry↗
NASA NTRS2019

Titan's Ionospheric Chemistry, Fullerenes, Oxygen, Galactic Cosmic Rays and the Formation of Exobiological Molecules on and within its Surfaces and Lakes

We discuss the formation of aerosols within Titan's thermosphere-ionosphere and the different chemical pathways. Negative ion measurements by the Cassini Plasma Spectrometer (CAPS) Electron Spectrometer (ELS) give evidence for formation of unsaturated anion carbon chains, while positive ion measurements of the Cassini Ion Neutral Mass Spectrometer (INMS) indicate formation of more aromatic cation hydrocarbons. There is presently no direct observational evidence for large neutral molecule growth in Titan's thermosphere-ionosphere. The hydrocarbon cations are expected to form Polycyclic Aromatic Hydrocarbons (PAH), those with the addition of nitrogen being called PAHNs. We theorize anion carbon chains can eventually become long enough to fold into fullerene C(60,70) carbon shells, of various charge states. Based on laboratory data the fullerenes can trap incoming O(sup +) magnetospheric ions that have relatively high energy collisions with the fullerenes and, once trapped, protect the oxygen atom from Titan's reducing thermosphere-ionosphere. The fullerenes can form into larger onion fullerenes and condense into larger embryo aerosols (i.e., m/q > 10,000 amu/q anions as observed by CAPS/ELS) eventually falling onto Titan's surface and precipitating to the bottom of its hydrocarbon lakes. Molecule production composed of H, C, N is known to occur in Titan's atmosphere with energy input from the magnetosphere, solar UV, and deeppenetrating irradiation from galactic cosmic rays (GCR). Space radiation effects by GCR irradiation of Titan's surface and lakes can lead to the manufacture of exobiological molecules with oxygen as the new ingredient. We have developed a model of galactic cosmic ray irradiation of Titan's atmosphere, surface, subsurface and bottoms of Titan lakes. GCR would provide further energy for processing of the aerosols into more complex organic forms such as tholins and precursor molecules for amino acids. A second process called hydrolysis then converts the precursor molecules into amino acids. Hydrolysis is provided via meteor impacts with size > 10 km and cryovolcanism both which can produce liquid water on Titan's surface for episodic periods > several 100 to 1000 years. Our model shows that GCR secondary particles can penetrate ~ 100 m below the ice surface (including the bottom of Titan's less dense hydrocarbon lakes ~ 150 m depths) and produce chemically significant dosages over very long timescales ~ 450 Myrs. The GCR model is combined with laboratory data from experiments in which dry methyl ices were irradiated to doses producing prebiotic amino acids such as glycine. The model calculations show glycine can form to ~ 2.5 ppb levels near the surface after ~450 Myrs of GCR proton irradiation and potentially to 5 ppb if heavy-ion GCRs up through Fe are included. If such molecules were detected, this would not only confirm this model but indicate that life forms different from ours may not be required.

Edward C. Sittler Jr↗
DOE OSTI2021

D-Band EPR and ENDOR Spectroscopy of 15 N-Labeled Photosystem I

For billions of years, nature has optimized the photosynthetic machinery that converts light energy into chemical energy. Key primary reactions of photosynthesis occur in large membrane protein-cofactor complexes. The light-induced sequential electron transfer reactions occur through a chain of donor/acceptor cofactors embedded in the protein matrix resulting in a long-lived transmembrane charge-separated state. EPR is the method of choice to study electron transfer and the interaction of protein environment with redox-active cofactors. However, the spectra of organic cofactor radicals typically are not fully resolved and severely overlap at conventional X-band EPR. Even at Q-band EPR, this overlap is present and often a serious problem. As a result, there is a large variation of the reported EPR data and limited understanding of electronic structures of several redox-active cofactors. These serious problems can often be overcome by the excellent spectral resolution provided by high-frequency EPR (HF EPR). In this work, we study the electronic structure of the primary electron donor P 700 and the secondary electron acceptor A 1 of Photosystem I (PSI) using 130 GHz (D-band) EPR and Electron-Nuclear-Double-Resonance (ENDOR) spectroscopy. PSI was isotopically labeled with 15 N (I = $\frac{1/2}$) to avoid quadrupolar interactions in the most abundant nitrogen isotope 14 N (I = 1) and simplify the ENDOR spectra. ENDOR spectroscopy is central for determining the hyperfine coupling of nitrogen atoms of the two chlorophyll molecules comprising oxidized P 700 and the involvement of protein nitrogen atoms with reduced A 1 . While HF ENDOR of A 1 - allows identification of two nitrogen atoms, HF ENDOR of P 700 + still does not permit unique assignment of the recorded hyperfine couplings.

15N↗
DOE OSTI2023

Using taxa-based approaches to delineate stream macroinvertebrate assemblage responses to stressor gradients in modified alluvial agroecosystems

Alluvial plain landscapes are some of the most agriculturally productive lands in the world but often have modified stream ecosystems due to cultivation history. This context requires consideration when establishing water quality management goals. We analyzed state water quality databases to demonstrate that Mississippi Alluvial Plain (MAP) ecoregion streams have elevated specific conductivity (SC) and nutrients and lower macroinvertebrate local and regional taxa pools compared to streams in other ecoregions, potentially reducing the efficacy of traditional biomonitoring approaches within the region. To overcome these challenges, we used threshold indicator taxa analysis (TITAN) to compare macroinvertebrate assemblage responses to water quality gradients among ecoregions in Mississippi. We identified individual taxa and assemblage-level responses to increasing water quality degradation in MAP streams. Observed responses occurred at higher concentrations for SC, total organic carbon (TOC) and total phosphorus (TP), but not total nitrogen (TN) relative to other ecoregions. These responses appeared to be driven by a large proportion of indicator taxa considered tolerant or unresponsive in other ecoregions, responding negatively to increasing water quality stressors in MAP streams. Our observed assemblage-level stressor responses to WQ gradients in MAP streams demonstrate shifting tolerance in highly altered ecosystems may require adjustments to recovery expectations but also provide useful measures for monitoring improvements in regional water quality. For example, our observed macroinvertebrate assemblage response to increasing TP identified a management goal similar to guidance based on distributional analysis of water quality data within the MAP ecoregion (0.11 vs 0.128 mg L –1 ) and thus provide some biological basis for previously identified nutrient goals for the region. Our approach can guide and monitor success of nutrient reduction efforts in MAP watersheds and other alluvial plain agroecosystems where reference conditions do not exist, and local and regional taxa pools are less diverse and may not support full recovery of ecological assemblages. While our results are promising, they should also be compared with more sensitive and less habitat-limited biological assemblages (e.g., algae or bacteria) to better understand complex ecological responses to best management practices designed to increase sustainability of high production agricultural regions.

59 BASIC BIOLOGICAL SCIENCES↗
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↗
DOE OSTI2024

Marine aerosol generation experiments in the High Arctic during summertime

The rapidly warming Arctic has transitioned to thinner sea ice which fractures, producing leads. Few studies have investigated Arctic sea spray aerosol (SSA) produced from open ocean, leads, and melt ponds, which vary in salinity and organic and microbial community composition. A marine aerosol reference tank was deployed aboard an icebreaker to the Arctic Ocean during August–September 2018 to study SSA generated from locally collected surface waters. Aerosol generation experiments were carried out using water collected from the marginal ice zone, a human-made hole in sea ice near the North Pole, and both lead and melt pond water during an ice floe drift period. Salinity, chlorophyll a, organic carbon, nitrogen, and microbial community composition were measured. Eukaryotic plankton and bacterial abundance were elevated in experimental water from the marginal ice zone, but the relative contributions from major eukaryotic taxonomic groups varied little across the experiments. The chemical composition of individual SSA particles was analyzed using Raman microspectroscopy and computer-controlled scanning electron microscopy with energy-dispersive X-ray spectroscopy. Individual sea salt aerosol, primary organic aerosol, and mineral dust particles were observed. Sea salt aerosol constituted 44–95% of individual submicrometer and 68–100% of supermicrometer particles, by number, generated during each experiment. Carbon was detected in 85%, by number, of the individual sea salt particles, with visible organic coatings. Carbohydrates were detected in 72% of particles, by number, with smaller contributions from long-chain fatty acids (13%) and siliceous material (15%). SSA generated from melt pond water contained only long-chain fatty acids and siliceous material. Quantification of the ice-nucleating activity showed that locally produced SSA may define the High Arctic background ice-nucleating particle population, but cannot account for the peak atmospheric concentrations observed. As the Arctic warms, the increasing SSA emissions have a complex dependence on changing biological and physical processes.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRSDate not supplied

Aerothermal Analysis of the Dragonfly Titan Entry

The Dragonfly mission will send a rotorcraft lander to the surface of Saturn’s moon Titan as part of the New-Frontiers program. This will be the first spacecraft to land on Titan since the Huygens probe’s descent in January of 2005 and only the second spacecraft to enter Titan’s atmosphere. The Dragonfly entry capsule is significantly larger than the Huygens probe and will experience higher aerothermal environments. This poster will provide an overview of the aerothermodynamic models used in the Dragonfly aeroshell design process. Titan provides a unique entry environment that has several fundamental differences from the environments at the more common entry destinations of Earth and Mars. The lack of atmospheric oxygen significantly reduces heatshield recession (expected to be negligible), which simplifies material response analysis but also reduces the efficiency of the thermal protection system. The atmos-phere is composed of mostly nitrogen and trace amounts of methane. During hypersonic entry this methane dissociates and leads to the formation of the molecule CN, which is known to radiate strongly in the shock layer. Current Dragonfly heating predictions estimate that radiation contributes about 50% of the total heat flux along the forebody and up to 90% on the aftbody, making radiation a key element of aerothermal analysis. To properly address the importance of radiation, a unique radiative-heating correlation was developed that incorporates normal-shock equilibrium chemistry predictions based on work from the Mars 2020 program. These new heating correlations agree well with Computational Fluid Dynamics (CFD) predictions and enable large-scale trajectory analyses by providing rapid heating predictions along candidate trajectories. Dragonfly aerothermal environments are generated with the Data Parallel Line Relaxation (DPLR) finite-volume Navier-Stokes solver alongside the Nonequilibrium Radiative Transport and Spectra (NEQAIR) radiation transport code. DPLR produces shock-aligned flowfields that incorporate the effects of both chemical and thermal nonequilibrium while NEQAIR solves the radiation transport equations along lines-of-sight through the flowfield solutions to predict the radiative heating on the aeroshell. Titan’s atmosphere produces complex thermal and chemical nonequilibria and so classical radiation approximations that extrapolate from a single line-of-sight, such as the Tangent-Slab method, were found to overpredict peak radiative heat fluxes by 10-20%. Therefore, all radiative heating is directly calculated using 3-D transport for both the forebody and aftbody to reduce unnecessary conservatism. A 21-species finite-rate chemistry model, including electrons and ionized species, is used in the CFD to ensure accurate vehicle heating predictions (the level of ionization is particularly for accurate radiative flux predictions). This poster will cover: 1) The models and assumptions used to simulate entry into Titan’s atmosphere, 2) Dragonfly aerothermal engineering correlations alongside statistical heating values, and 3) Driving aerothermal considerations for a Titan entry such as CN formation and radiation-flowfield coupling.

EDL↗
NASA NTRS2013

Reducing Organic Contamination in NASA JSC Astromaterial Curation Facility

Future robotic and human spaceflight missions to the Moon, Mars, asteroids and comets will require handling and storing astromaterial samples with minimal inorganic and organic contamination to preserve the scientific integrity of each sample. Much was learned from the rigorous attempts to minimize and monitor organic contamination during Apollo, but it was not adequate for current analytical requirements; thus [1]. OSIRIS-REx, Hayabusa-2, and future Mars sample return will require better protocols for reducing organic contamination. Future isolation con-tainment systems for astromaterials, possibly nitrogen enriched gloveboxes, must be able to reduce organic and inorganic cross-contamination. In 2012, a baseline study established the current state of organic cleanliness in gloveboxes used by NASA JSC astromaterials curation labs that could be used as a benchmark for future mission designs [2, 3]. After standard ultra-pure water (UPW) cleaning, the majority of organic contaminates found were hydrocarbons, plasticizers, silicones, and solvents. Hydro-carbons loads (> C7) ranged from 1.9 to 11.8 ng/cm2 for TD-GC-MS wafer exposure analyses and 5.0 to 19.5 ng/L for TD-GC-MS adsorbent tube exposure. Plasticizers included < 0.6 ng/cm2 of DBP, DEP, TXIB, and DIBP. Silicones included < 0.5 ng/cm2 of cyclo(Me2SiO)x (x = 6, 8, 9, 10) and siloxane. Solvents included < 1.0 ng/cm2 of 2-cyclohexen-1-one, 3,5,5-trimethyl- (Isopho-rone), N-formylpiperidine, and 2-(2-butoxyethoxy) ethanol. In addition, DBF, rubber/polymer additive was found at < 0.2 ng/cm2 and caprolactam, nylon-6 at < 0.6 ng/cm2. Reducing Organics: The Apollo program was the last sam-ple return mission to place high-level organic requirements and biological containment protocols on a curation facility. The high vacuum complex F-201 glovebox in the Lunar Receiving Labora-tory used ethyl alcohol (190 proof), 3:1 benzene/methanol (nano grade solution), and heat sterilization at 130degC for 48 hours to reduce organic contamination. In addition, both heat sterilization and peracetic acid sterilization were used in the atmospheric de-contamination (R) cabinets. Later, Lunar curation gloveboxes were degreased with a pressurized Freon 113 wash. Today, UPW has replaced Freon as the standard cleaning procedure, but does not have the degreasing solvency power of Freon. Future Cleaning Studies: Cleaning experiments are cur-rently being orchestrated to study how to degrease and reduce organics in a JSC curation glovebox lower than the established baseline. Several new chemicals in the industry have replaced traditional degreasing solvents such as Freon and others that are now federally restricted. However, these new suites of chemicals remain untested for lowering organics in curation gloveboxes. 3M's HFE-7100DL and DuPont's Vertrel XF are currently being tested as a replacement for Freon 113 as a degreaser at JSC cura-tion facilities. In addition, the use of UPW as a final rinse is be-ing tested, which presumably can maintain a lower total organic carbon load than the filtered purity of chemical solutions. References: [1] Allton J.H. et al. (2012) LPS XLIII, 2439; [2] Calaway M.

Calaway, M. J.↗
DOE OSTI2022

Effect of silver($\mathrm{I}$) ion reduction on the selectivity of olefins, paraffins, and aromatic compounds by gas chromatographic stationary phases consisting of silver($\mathrm{I}$) salts in ionic liquids

We report the olefin/paraffin selectivity offered by ionic liquid (IL) stationary phases can be enhanced through the addition of silver(I) ion, which is well-known to undergo selective complexation with unsaturated compounds. However, such stationary phases often suffer from the loss of chromatographic selectivity as silver(I) ion can be reduced to elemental silver. To maintain the separation performance of silver(I) ion/IL stationary phases, an understanding of factors and conditions that promote the reduction of silver(I) ion is needed. In this study, capillary gas chromatography columns featuring a stationary phase consisting of the 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C 10 MIM + ][NTf 2 - ]) IL impregnated with [Ag + ][NTf 2 - ] were examined to investigate the effects of temperature, hydrogen content in exposure gas stream, and time of heating/exposure events on olefin selectivity. Retention factors of representative analytes, such as C 6 olefins and paraffins as well as aromatic compounds, were measured after subjecting the columns to the aforementioned conditions, followed by an evaluation of selectivity factors over time. Selectivity factors of olefins and aromatic compounds were observed to decrease significantly when the stationary phases were heated to temperatures higher than 110°C as well as being subjected to mixed gas streams containing greater than 50 mol% of hydrogen. As constant column heating temperatures were applied under exposure gas mixtures containing hydrogen and nitrogen, a gradual decrease in analyte selectivity factors was observed under prolonged periods of time. However, application of a ternary gas mixture comprised of 25/50/25 mol% hydrogen/nitrogen/methane resulted in an increase in the 3-hexyne/cis-2-hexene selectivity when measured at 120°C for 60 h, due to a smaller decrease in the retention factor of 3-hexyne compared to cis-2-hexene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

Far UV camera/spectrograph

In March 1610, Galileo Galilei reported the first use of a telescope to view mountains and maria on the Moon. On April 21, 1972, the Apollo 16 commander pointed a somewhat more complex optical instrument at the Earth from the Moon and obtained several remarkable photographs showing atmospheric rather than surface features. The optical part of the far UV camera (aperture, 7.5 cm) was not much larger than Galileo's telescope. Like his, this instrument was also pointed at other celestial objects that Galileo viewed, including the Milky Way and Jupiter, and the Large Magellanic Cloud (LMC), which is not visible from Italy. More important, the far UV camera/spectrograph recorded light in the invisible band of wavelengths between 50 and 160 nm, approximately one-third the wavelength that can penetrate the atmosphere of the Earth to ground-based telescopes. As described in more detail in this section, these UV observations from the Moon allow study of the entire atmosphere of the Earth and the geocorona. The photographs show hydrogen and other gases in the solar wind and interplanetary media, and they provide new data on stars, nebulae, and galaxies much farther away. When used as a spectrograph, the instrument distributes the light it receives according to wavelength, and the resulting spectrum shows bright lines or gaps known to be characteristic of various gases, such as hydrogen (H), helium (He), oxygen (O), nitrogen (N), and neon (Ne). If a gas cloud is hot, the atoms are excited and the spectrum shows bright emission lines; if it is cool, the atoms absorb light, leaving gaps or absorption lines. The far UV camera is blind to ordinary visible light; for that reason, the photographs show very few of the stars mapped by ground-based telescopes. Only the very-high-temperature (blue) stars of spectral classes O, B, and possibly A (temperatures from 50000 ° down to 10000°K) are expected to be recorded. Image blackness or density on the negatives also depends on the brightness of the star, which astronomers measure in an inverted logarithmic scale of magnitudes. A star of 6 magnitudes (mag.) can barely be seen with the unaided eye. An 11-mag. star is 100 times fainter, and a 12-mag. star is 2.5 times fainter yet. The faintest star recorded by the far UV camera is at least 11 mag., which is called the limiting magnitude.

George R. Carruthers↗
NASA NTRS1989

Multiplex gas chromatography: an alternative concept for gas chromatographic analysis of planetary atmospheres

Gas chromatography (GC) is a powerful technique for analyzing gaseous mixtures. Applied to the earth's atmosphere, GC can be used to determine the permanent gases--such as carbon dioxide, nitrogen, and oxygen--and to analyze organic pollutants in air. The U.S. National Aeronautics and Space Administration (NASA) has used GC in spacecraft missions to Mars (the Viking Biology Gas Exchange Experiment [GEX] and the Viking Gas Chromatograph-Mass Spectrometer [GC-MS]) and to Venus (the Pioneer Venus Gas Chromatograph [PVGC] on board the Pioneer Venus sounder probe) for determining the atmospheric constituents of these two planets. Even though conventional GC was very useful in the Viking and Pioneer missions, spacecraft constraints and limitations intrinsic to the technique prevented the collection of more samples. With the Venus probe, for instance, each measurement took a relatively long time to complete (10 min), and successive samples could not be introduced until the previous samples had left the column. Therefore, while the probe descended through the Venusian atmosphere, only three samples were acquired at widely separated altitudes. With the Viking mission, the sampling rate was not a serious problem because samples were acquired over a period of one year. However, the detection limit was a major disadvantage. The GC-MS could not detect simple hydrocarbons and simple alcohols below 0.1 ppm, and the GEX could not detect them below 1 ppm. For more complex molecules, the detection limits were at the parts-per-billion level for both instruments. Finally, in both the Viking and Pioneer missions, the relatively slow rate of data acquisition limited the number of analyses, and consequently, the amount of information returned. Similar constraints are expected in future NASA missions. For instance, gas chromatographic instrumentation is being developed to collect and analyze organic gases and aerosols in the atmosphere of Titan (one of Saturn's satellites). The Titan-Cassini entry probe, which is being jointly planned by NASA and the European Space Agency (ESA), might be launched as early as 1994. As in the Pioneer mission, limited time--perhaps only 3-4 h--will be available for the completion of all analyses while the probe descends through the atmosphere. A conventional GC or GC-MS system would be able to analyze no more than two aerosol and two gas samples during the probe's descent. Conventional GC also is limited by the sensitivity of the detector and by the sample volume. For the Titan mission, the sensitivity problems will be worse because the atmospheric pressure at the time of instrument deployment is expected to be < 3 torr. Consequently, the sample volume might not be large enough to satisfy the detector sensitivity requirements. Because of such limitations, alternative GC analysis techniques have been investigated for future NASA missions. Multiplex gas chromatography has been investigated as a possible candidate for chemical analysis within a spacecraft or other restricted environment, and chemical modulators have been developed and used when needed with this technique to reduce the size and weight of the instrumentation. Also, several new multiplex techniques have been developed for use in specific applications.

NASA Center ARC↗
DOE OSTI2021

NPRL2 reduces the niraparib sensitivity of castration-resistant prostate cancer via interacting with UBE2M and enhancing neddylation

In this study, we explored the regulatory effects of nitrogen permease regulator 2-like (NPRL2) on niraparib sensitivity, a PARP inhibitor (PARPi) in castrate-resistant prostate cancer (CRPC). Data from The Cancer Genome Atlas (TCGA) and Genotype-Tissue Expression (GTEx) program were retrospectively examined. Gene-set enrichment analysis (GSEA) was conducted between high and low NRPL2 expression prostate adenocarcinoma (PRAD) cases in TCGA. CCK-8 assay, Western blot analysis of apoptotic proteins, and flow cytometric analysis of apoptosis were applied to test niraparib sensitivity. Immunofluorescent (IF) staining and co-immunoprecipitation (co-IP) were conducted to explore the proteins interacting with NPRL2. Results showed that the upregulation of a canonical protein-coding transcript of NPRL2 (ENST00000232501.7) is associated with an unfavorable prognosis. Bioinformatic analysis predicts a physical interaction between NPRL2 and UBE2M, which is validated by a following Co-IP assay. This interaction increases NPRL2 stability by reducing polyubiquitination and proteasomal degradation. Depletion of NPRL2 or UBE2M significantly increases the niraparib sensitivity of CRPC cells and enhances niraparib-induced tumor growth inhibition in vivo. NPRL2 cooperatively enhances UBE2M-mediated neddylation and facilitates the degradation of multiple substrates of Cullin-RING E3 ubiquitin ligases (CRLs). In conclusion, this study identified a novel NPRL2-UBE2M complex in modulating neddylation and niraparib sensitivity of CRPC cells. Therefore, targeting NPRL2 might be considered as an adjuvant strategy for PARPi therapy.

60 APPLIED LIFE SCIENCES↗
NASA NTRS2020

Titan's Ionospheric Chemistry, Fullerenes, Oxygen, Galactic Cosmic Rays and the Formation of Exobiological Molecules on and Within Its Surfaces and Lakes

We discuss the formation of aerosols within Titan's thermosphere-ionosphere and the different chemical pathways. Negative ion measurements by the Cassini Plasma Spectrometer (CAPS) Electron Spectrometer (ELS) give evidence for formation of unsaturated anion carbon chains, while positive ion measurements of the Cassini Ion Neutral Mass Spectrometer (INMS) indicate formation of more aromatic cation hydrocarbons. There is presently no direct observational evidence for large neutral molecule growth in Titan's thermosphere-ionosphere. The hydrocarbon cations are expected to form Polycyclic Aromatic Hydrocarbons (PAHs), those with the addition of nitrogen being called PAHNs. We theorize anion carbon chains can eventually become long enough to fold into fullerene C60,70 carbon shells, of various charge states. Based on laboratory data the fullerenes can trap incoming O+ magnetospheric ions that have relatively high energy collisions with the fullerenes and, once trapped, protect the oxygen atom from Titan's reducing thermosphere-ionosphere. The fullerenes can form into larger onion fullerenes and condense into larger embryo aerosols (i.e., m/q (mass-to-charge ratio) greater than 10,000 amu/q (atomic mass unit-to-charge ratio) anions as observed by CAPS/ELS) eventually falling onto Titan's surface and precipitating to the bottom of its hydrocarbon lakes. Molecule production composed of H, C, N is known to occur in Titan's atmosphere with energy input from the magnetosphere, solar UV (ultraviolet), and deep-penetrating irradiation from galactic cosmic rays (GCR). Space radiation effects by GCR irradiation of Titan's surface and lakes can lead to the manufacture of exobiological molecules with oxygen as the new ingredient. We have developed a model of galactic cosmic ray irradiation of Titan's atmosphere, surface, subsurface and bottoms of Titan lakes. GCR would provide further energy for processing of the aerosols into more complex organic forms such as tholins and precursor molecules for amino acids. A second process called hydrolysis then converts the precursor molecules into amino acids. Hydrolysis is provided via meteor impacts with size greater than 10 kilometers and cryovolcanism both which can produce liquid water on Titan's surface for episodic periods more than several 100 to 1000 years. Our model shows that GCR secondary particles can penetrate ~100 meters below the ice surface (including the bottom of Titan's less dense hydrocarbon lakes ~150-meter depths) and produce chemically significant dosages over very long timescales ~450 million years. The GCR model is combined with laboratory data from experiments in which dry methyl ices were irradiated to doses producing prebiotic amino acids such as glycine. The model calculations show glycine can form to ~2.5 parts-per-billion levels near the surface after ~450 million years of GCR proton irradiation and potentially to 5 parts-per-billion if heavy-ion GCRs up through Fe are included. If such molecules were detected, this would not only confirm this model but indicate that life forms different from ours may not be required.

Edward C. Sittler Jr↗
NASA NTRS2012

Active Upper-atmosphere Chemistry and Dynamics from Polar Circulation Reversal on Titan

Saturn's moon Titan has a nitrogen atmosphere comparable to Earth's, with a surface pressure of 1.4 bar. Numerical models reproduce the tropospheric conditions very well but have trouble explaining the observed middle-atmosphere temperatures, composition and winds. The top of the middle-atmosphere circulation has been thought to lie at an altitude of 450 to 500 kilometres, where there is a layer of haze that appears to be separated from the main haze deck. This 'detached' haze was previously explained as being due to the colocation of peak haze production and the limit of dynamical transport by the circulation's upper branch. Herewe report a build-up of trace gases over the south pole approximately two years after observing the 2009 post-equinox circulation reversal, from which we conclude that middle-atmosphere circulation must extend to an altitude of at least 600 kilometres. The primary drivers of this circulation are summer-hemisphere heating of haze by absorption of solar radiation and winter-hemisphere cooling due to infrared emission by haze and trace gases; our results therefore imply that these effects are important well into the thermosphere (altitudes higher than 500 kilometres). This requires both active upper-atmosphere chemistry, consistent with the detection of high-complexity molecules and ions at altitudes greater than 950 kilometres, and an alternative explanation for the detached haze, such as a transition in haze particle growth from monomers to fractal structures.

Titan Atmosphere↗