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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1999

Atmospheric pressure chemical ionization of fluorinated phenols in atmospheric pressure chemical ionization mass spectrometry, tandem mass spectrometry, and ion mobility spectrometry

Atmospheric pressure chemical ionization (APCI)-mass spectrometry (MS) for fluorinated phenols (C6H5-xFxOH Where x = 0-5) in nitrogen with Cl- as the reagent ion yielded product ions of M Cl- through ion associations or (M-H)- through proton abstractions. Proton abstraction was controllable by potentials on the orifice and first lens, suggesting that some proton abstraction occurs through collision induced dissociation (CID) in the interface region. This was proven using CID of adduct ions (M Cl-) with Q2 studies where adduct ions were dissociated to Cl- or proton abstracted to (M-H)-. The extent of proton abstraction depended upon ion energy and structure in order of calculated acidities: pentafluorophenol > tetrafluorophenol > trifluorophenol > difluorophenol. Little or no proton abstraction occurred for fluorophenol, phenol, or benzyl alcohol analogs. Ion mobility spectrometry was used to determine if proton abstraction reactions passed through an adduct intermediate with thermalized ions and mobility spectra for all chemicals were obtained from 25 to 200 degrees C. Proton abstraction from M Cl- was not observed at any temperature for phenol, monofluorophenol, or difluorophenol. Mobility spectra for trifluorophenol revealed the kinetic transformations to (M-H)- either from M Cl- or from M2 Cl- directly. Proton abstraction was the predominant reaction for tetra- and penta-fluorophenols. Consequently, the evidence suggests that proton abstraction occurs from an adduct ion where the reaction barrier is reduced with increasing acidity of the O-H bond in C6H5-xFxOH.

NASA Discipline Environmental Health↗
NASA NTRS2016

Tandem Mass Spectrometry on a Miniaturized Laser Desorption Time-of-Flight Mass Spectrometer

Tandem mass spectrometry (MSMS) is a powerful and widely-used technique for identifying the molecular structure of organic constituents of a complex sample. Application of MSMS to the study of unknown planetary samples on a remote space mission would contribute to our understanding of the origin, evolution, and distribution of extraterrestrial organics in our solar system. Here we report on the realization of MSMS on a miniaturized laser desorption time-of-flight mass spectrometer (LD-TOF-MS), which is one of the most promising instrument types for future planetary missions. This achievement relies on two critical components: a curved-field reflectron and a pulsed-pin ion gate. These enable use of the complementary post-source decay (PSD) and laser-assisted collision induced dissociation (L-CID) MSMS methods on diverse measurement targets with only modest investment in instrument resources such as volume and weight. MSMS spectra of selected molecular targets in various organic standards exhibit excellent agreement when compared with results from a commercial, laboratory-scale TOF instrument, demonstrating the potential of this powerful technique in space and planetary environments.

Li, Xiang↗
NASA NTRS1990

Prebiotic synthesis of histidine

The prebiotic formation of histidine (His) has been accomplished experimentally by the reaction of erythrose with formamidine followed by a Strecker synthesis. In the first step of this reaction sequence, the formation of imidazole-4-acetaldehyde took place by the condensation of erythrose and formamidine, two compounds that are known to be formed under prebiotic conditions. In a second step, the imidazole-4-acetaldehyde was converted to His, without isolation of the reaction products by adding HCN and ammonia to the reaction mixture. LC, HPLC, thermospray liquid chromatography-mass spectrometry, and tandem mass spectrometry were used to identify the product, which was obtained in a yield of 3.5% based on the ratio of His/erythrose. This is a new chemical synthesis of one of the basic amino acids which had not been synthesized prebiotically until now.

Non-NASA Center↗
NASA NTRS1986

Determination of cosmogenic Ca-41 in a meteorite with tandem accelerator mass spectrometry

The first use of tandem accelerator mass spectrometry (TAMS) to measure the content of Ca-41 in a natural sample, the iron Bogou meteorite, is reported. Ca in the samples was extracted by hydroxide precipitation and purified by means of a caution exchange resin (AG 50W-X8). After adding 4 percent ammonium oxide, the precipitate was ignited to CaO in a quartz vial at about 1100 C. The Ca-41/Ca ratios were determined following acceleration by alternate measurements of the Ca-40 beam current in an image Faraday cup. Ca-41 particles were also measured using a gas counter. The measured Ca-41/Ca ratio was 3.8 + or -0.6 x 10 to the 12th, which corresponds to a Ca-41 activity of 6.9 + or -1.1 d.p.m. per kg. Calculation of the half-life of Ca-41 in the Bogou meteorite yielded an age of 103,000 years.

Kubik, P. W.↗
NASA NTRS1980

Half-life of Si-32 from tandem-accelerator mass spectrometry

A newly developed mass-spectrometry technique employing a tandem Van de Graaff accelerator together with a special beam-transport system and heavy-ion detector has been used to determine the half-life of Si-32. The result obtained, 108 plus or minus 18 yr, disagrees with the accepted value of 330 plus or minus 40 yr. The implications of the new half-life of Si-32, which is used for dating studies, are discussed.

Elmore, D.↗
NASA NTRS1983

Measurements of I-129 in meteorites and lunar rock by tandem accelerator mass spectrometry

Precise measurements of the half-life of I-129 in three different meteorites and one lunar surface rock are reported. The meteorite source of I-129 was produced by cosmic ray secondary neutron reactions on Te, while the source in lunar materials in spallation on barium and rare earth elements. The Abee, Allende, and Dhajala meteorites were examined, together with the lunar rock 14310. Details of the process used to extract the iodine are provided. The Abee and Allende samples exhibited a production of 0.5 atom/min per gm of Te from the (n,2n) reaction and 0.05 atom/min/gm for the (n,gamma) reaction. The I-129 is concluded to be a viable tool for long-lived cosmogenic nuclide studies. Further work to extend the data to include the constancy of the cosmic ray flux, the meteorite bombardment history, and the cosmic exposure age dating by means of the I-129 and Xe-129 method is indicated.

Nizhiizumi, K.↗
NASA NTRS1984

C-14 content of ten meteorites measured by tandem accelerator mass spectrometry

Measurements of C-14 in three North American and seven Antarctic meteorites show in most cases that this cosmogenic isotope, which is tightly bound, was separated from absorbed atmospheric radiocarbon by stepwise heating extractions. The present upper limit to age determination by the accelerator method varies from 50,000 to 70,000 years, depending on the mass and carbon content of the sample. The natural limit caused by cosmic ray production of C-14 in silicate rocks at 2000 m elevation is estimated to be 55,000 + or - 5000 years. An estimation is also made of the 'weathering ages' of the Antarctic meteorites from the specific activity of loosely bound CO2 which is thought to be absorbed from the terrestrial atmosphere. Accelerator measurements are found to agree with previous low level counting measurements, but are more sensitive and precise.

Brown, R. M.↗
NASA NTRS2015

In Situ Detection of Organic Molecules on the Martian Surface With the Mars Organic Molecule Analyzer (MOMA) on Exomars 2018

The Mars Organic Molecule Analyzer (MOMA) investigation on the 2018 ExoMars rover will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from radiative and oxidative degradation. The MOMA instrument is centered around a miniaturized linear ion trap (LIT) that facilitates two modes of operation: i) pyrolysisgas chromatography mass spectrometry (pyrGC-MS); and, ii) laser desorptionionization mass spectrometry (LDI-MS) at ambient Mars pressures. The LIT also enables the structural characterization of complex molecules via complementary analytical capabilities, such as multi-frequency waveforms (i.e., SWIFT) and tandem mass spectrometry (MSMS). When combined with the complement of instruments in the rovers Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds.

ExoMars2018↗
NASA NTRS1995

Monitoring Trace Contaminants in Air Via Ion Trap Mass Spectrometry

Recent passage of the Clean Air Act with its stricter regulation of toxic gas emissions, and the ever-growing number of applications which require faster turnaround times between sampling and analysis are two major factors which are helping to drive the development of new instrument technologies for in-situ, on-line, real-time monitoring. The ion trap, with its small size, excellent sensitivity, and tandem mass spectrometry capability is a rapidly evolving technology which is well-suited for these applications. In this paper, we describe the use of a commercial ion trap instrument for monitoring trace levels of chlorofluorocarbons (CFCs) and volatile organic compounds (VOCs) in air. A number of sample introduction devices including a direct transfer line interface, short column GC, and a cryotrapping interface are employed to achieve increasing levels of sensitivity. MS, MS/MS, and MS/MS/MS methods are compared to illustrate trade-offs between sensitivity and selectivity. Filtered Noise Field (FNF) technology is found to be an excellent means for achieving lower detection limits through selective storage of the ion(s) of interest during ionization. Figures of merit including typical sample sizes, detection limits, and response times are provided. The results indicate the potential of these techniques for atmospheric assessments, the High Speed Research Program, and advanced life support monitoring applications for NASA.

Palmer, Peter T.↗
NASA NTRS2015

Design and Demonstration of the Mars Organic Molecule Analyzer (MOMA) on the ExoMars 2018 Rover

The Mars Organic Molecule Analyzer (MOMA) investigation is a key astrobiology experiment scheduled to launch on the joint ESA-Roscosmos ExoMars 2018 rover mission. MOMA will examine the chemical composition of geological samples acquired from depths of up to two meters below the martian surface, where fragile organic molecules may be protected from destructive cosmic radiation and/or oxidative chemical reactions. The heart of the MOMA mass spectrometer subsystem (i.e., MOMA-MS) is a miniaturized linear ion trap (LIT) that supports two distinct modes of operation to detect: i) volatile and semi-volatile, low-to-moderate mass organics (less than or equal to 500 Da) via pyrolysis coupled with gas chromatography mass spectrometry (pyr/GCMS); and, ii) more refractory, moderate-to-high mass compounds (up to 1000 Da) via laser desorption (LDMS) at ambient Mars pressures. Additionally, the LIT mass analyzer enables selective ion trapping via multi-frequency waveform ion excitation (e.g., stored waveform inverse Fourier transform, or SWIFT), and structural characterization of complex molecules using tandem mass spectrometry (MSIMS). A high-fidelity Engineering Test Unit (ETU) of MOMAMS, including the LIT subassembly, dual-gun electron ionization source, micropirani pressure gauge, solenoid-driven aperture valve, redundant detection chains, and control electronics, has been built and tested at NASA GSFC under relevant operational conditions (pressure, temperature, etc.). Spaceflight qualifications of individual hardware components and integrated subassemblies have been validated through vibration, shock, thermal, lifetime, and performance evaluations. The ETU serves as a pathfinder for the flight model buildup, integration and test, as the ETU meets the form, fit and function of the flight unit that will be delivered to MPS in late 2015. To date, the ETU of MOMA-MS has been shown to meet or exceed all functional requirements, including mass range, resolution, accuracy, instrumental drift, and Iimit-of-detection specifications, thereby enabling the primary science objectives of the MOMA investigation and ExoMars 2018 mission.

Mars Organic Molecule Analyzer↗
NASA NTRS2017

Mars Organic Molecule Analyzer (MOMA) Laser Desorption/Ionization Source Design and Performance Characterization

The Mars Organic Molecule Analyzer (MOMA), a dual-source, ion trap-based instrument capable of both pyrolysis-gas chromatography mass spectrometry (pyr/GC-MS) and laser desorption/ionization mass spectrometry (LDI-MS), is the core astrobiology investigation on the ExoMars rover. The MOMA instrument will be the first spaceflight mass analyzer to exploit the LDI technique to detect refractory organic compounds and characterize host mineralogy; this mode of analysis will be conducted at Mars ambient conditions. In order to achieve high performance in the Martian environment while keeping the instrument compact and low power, a number of innovative designs and components have been implemented for MOMA. These include a miniaturized linear ion trap (LIT), a fast actuating aperture valve with ion inlet tube, and a Microelectromechanical System (MEMS) Pirani sensor. Advanced analytical capabilities like Stored Waveform Inverse Fourier Transform (SWIFT) for selected ion ejection and tandem mass spectrometry (MS/MS) are realized in LDI-MS mode, and enable the isolation and enhancement of specific mass ranges and structural analysis, respectively. We report here the technical details of these instrument components as well as system-level analytical capabilities, and we review the applications of this technology to Mars and other high-priority targets of planetary exploration.

Xiang Li↗
NASA NTRS2008

Miniature Mass Spectrometers on Space and Planetary Missions

Space flight mass spectrometers contribute our understanding of the origin and evolution of our solar system and even of life itself. This fundamental role has motivated increasing interest in miniature mass spectrometry for planetary missions. Several remarkable new instruments are en route or under development to investigate the composition of planetary bodies such as Mars and comets. For instance, the Sample Analysis at Mars (SAM) suite on the 2009 Mars Science Laboratory (MSL) mission includes a quadrupole mass spectrometer with a sophisticated gas processing system as well as pyrolysis and chemical derivatization protocols for solid samples. Future missions will require even lighter, lower power, and yet more capable mass spectrometers, particularly to analyze samples in situ on planetary surfaces. We have been developing laser-based mass spectrometers for elemental and organic/molecular analysis of rock, ice, or fine particle samples. These typically use time-of-flight (TOF) mass analyzers, which are readily miniaturized and can detect both atomic species and complex organics that occur in a variety of planetary materials. For example, nonvolatile polycyclic aromatic hydrocarbons and kerogen-like macromolecular carbon are found in some carbonaceous meteorites, which derived from asteroid parent bodies. A single focused laser pulse is able to volatilize and ionize some of these compounds for direct TOF analysis. While this is possible without any sample preparation or contact, sensitivity and quantitative performance can improve significantly with some sample handling. As such we have also been examining robotic mechanisms and protocols to accompany space flight mass spectrometers. In addition, sensors in early development may significantly improve these capabilities, via use of techniques such as switchable polarity, ambient pressure, or resonant ionization; tandem mass spectrometry (TOF or ion trap); and chemical imaging.

Brinckerhoff, William↗
NASA NTRS2005

Identification of transcribed sequences in Arabidopsis thaliana by using high-resolution genome tiling arrays

Using a maskless photolithography method, we produced DNA oligonucleotide microarrays with probe sequences tiled throughout the genome of the plant Arabidopsis thaliana. RNA expression was determined for the complete nuclear, mitochondrial, and chloroplast genomes by tiling 5 million 36-mer probes. These probes were hybridized to labeled mRNA isolated from liquid grown T87 cells, an undifferentiated Arabidopsis cell culture line. Transcripts were detected from at least 60% of the nearly 26,330 annotated genes, which included 151 predicted genes that were not identified previously by a similar genome-wide hybridization study on four different cell lines. In comparison with previously published results with 25-mer tiling arrays produced by chromium masking-based photolithography technique, 36-mer oligonucleotide probes were found to be more useful in identifying intron-exon boundaries. Using two-dimensional HPLC tandem mass spectrometry, a small-scale proteomic analysis was performed with the same cells. A large amount of strongly hybridizing RNA was found in regions "antisense" to known genes. Similarity of antisense activities between the 25-mer and 36-mer data sets suggests that it is a reproducible and inherent property of the experiments. Transcription activities were also detected for many of the intergenic regions and the small RNAs, including tRNA, small nuclear RNA, small nucleolar RNA, and microRNA. Expression of tRNAs correlates with genome-wide amino acid usage.

Arabidopsis/genetics↗
NASA NTRS1995

Deuterium Exchange in the Systems of H2O+/H2O and H3O+/H2O

Using tandem mass spectrometry various water ion interactions were observed. These reactions consisted of a series of charge transfer, proton transfer, and isotopic exchange steps. The experimental data sets consist of variations of ion abundances over a neutral pressure range. An expected sequence of isotopic exchange reactions is given along with differential equation solutions & reaction rate data.

Spectroscopy Deuterium Proton Ion Atmospheric Scie↗
NASA NTRS2010

Distinct Distribution of Purines in CM and CR Carbonaceous Chondrites

Carbonaceous meteorites contain a diverse suite of organic molecules and delivered pre biotic organic compounds, including purines and pyrimidines, to the early Earth (and other planetary bodies), seeding it with the ingredients likely required for the first genetic material. We have investigated the distribution of nucleobases in six different CM and CR type carbonaceous chondrites, including fivc Antarctic meteorites never before analyzed for nucleobases. We employed a traditional formic acid extraction protocol and a recently developed solid phase extraction method to isolate nucleobases. We analyzed these extracts by high performance liquid chromatography with UV absorbance detection and tandem mass spectrometry (HPLC-UV -MS/MS) targeting the five canonical RNAIDNA bases and hypoxanthine and xanthine. We detected parts-per-billion levels of nucleobases in both CM and CR meteorites. The relative abundances of the purines found in Antarctic CM and CR meteorites were clearly distinct from each other suggesting that these compounds are not terrestrial contaminants. One likely source of these purines is formation by HCN oligomerization (with other small molecules) during aqueous alteration inside the meteorite parent body. The detection of the purines adenine (A), guanine (0), hypoxanthine (HX), and xanthine (X) in carbonaceous meteorites indicates that these compounds should have been available on the early Earth prior to the origin of the first genetic material.

Callahan, Michael P.↗
NASA NTRS2016

Elucidating the Gravome: Quantitative Proteomic Profiling of the Response to Chronic Hypergravity in Drosophila

Altered gravity conditions, such as experienced by organisms during spaceflight, is known to cause transcriptomic and proteomic changes. We describe the proteomic changes in the whole body of adult Drosophila melanogaster (fruit fly), but focus specifically on the localized changes in the adult head in response to chronic hypergravity (3G) treatment. Canton S adult female flies (2-3 days old) were exposed to chronic hypergravity for 9 days and compared with parallel 1G controls. After hypergravity treatment, whole flies and fly heads were separated, and evaluated for quantitative comparison of the two gravity conditions using an isobaric tagging liquid chromatography-tandem mass spectrometry approach. Data revealed a total of 1948 (whole flies) and 1480 (head) proteins to be differentially present in hypergravity-treated flies. Gene Ontology analysis of head specific proteomics revealed host immune response and humoral stress proteins were significantly upregulated. Proteins related to calcium signaling, ion transport and ATPase were decreased. Enhanced expression of cuticular proteins may suggest an alteration in chitin metabolism and in chitin-based cuticle development. We therefore present a comprehensive quantitative survey of proteomic changes in response to chronic hypergravity in Drosophila, which will help elucidate the underlying molecular mechanisms associated with altered gravity environments.

Hypergravity↗
NASA NTRS1986

Radionuclide measurements by accelerator mass spectrometry at Arizona

Over the past years, Tandem Accelerator Mass Spectrometry (TAMS) has become established as an important method for radionuclide analysis. In the Arizona system the accelerator is operated at a thermal voltage of 1.8MV for C-14 analysis, and 1.6 to 2MV for Be-10. Samples are inserted into a cesium sputter ion source in solid form. Negative ions sputtered from the target are accelerated to about 25kV, and the injection magnet selects ions of a particular mass. Ions of the 3+ charge state, having an energy of about 9MeV are selected by an electrostatic deflector, surviving ions pass through two magnets, where only ions of the desired mass-energy product are selected. The final detector is a combination ionization chamber to measure energy loss (and hence, Z), and a silicon surface-barrier detector which measures residual energy. After counting the trace iosotope for a fixed time, the injected ions are switched to the major isotope used for normalization. These ions are deflected into a Faraday cup after the first high-energy magnet. Repeated measurements of the isotope ratio of both sample and standards results in a measurement of the concentration of the radionuclide. Recent improvements in sample preparation for C-14 make preparation of high-beam current graphite targets directly from CO2 feasible. Except for some measurements of standards and backgrounds for Be-10 measurements to date have been on C-14. Although most results have been in archaeology and quaternary geology, studies have been expanded to include cosmogenic C-14 in meteorites. The data obtained so far tend to confirm the antiquity of Antarctic meteorites from the Allan Hills site. Data on three samples of Yamato meteorites gave terrestrial ages of between about 3 and 22 thousand years.

Jull, A. J. T.↗