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Results for “MASS SPECTRA”

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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Molecular Characterization of High Molecular Weight Polyesters by Matrix-Assisted Laser Desorption/Ionization High-Resolution Time-of-Flight Mass Spectrometry Combined with On-plate Alkaline Degradation and Mass Defect Analysis

Matrix-assisted laser desorption ionization high-resolution time-of-flight mass spectrometry (MALDI HR TOF MS) is a powerful tool for the molecular characterization of industrial polymers. However, accurate mass determination and resolution of isobaric ions are possible for oligomer samples only typically below m/z 3000. To cut long polymer chains into oligomers suitable for high-resolution mass spectrometry, we propose a simple “on-plate” alkaline degradation of polyesters as a sample pretreatment technique prior to the MALDI TOF MS measurement. This pretreatment can be performed on a MALDI target using a small amount of sample (μg or less) and 1 μL of alkaline reagent by simple pipetting. Informative mass spectra in the oligomeric mass range are successfully recorded but complicated by the variation of end-groups and the copolymeric composition of the degradation products. Data processing is assisted by a series of advanced Kendrick mass defect (KMD) analyses recently proposed by the authors to plot visually understandable two-dimensional maps. On-plate degradation pretreatment, high-resolution MALDI TOF MS measurements, and advanced KMD analyses are innovatively combined for the compositional characterization of bacterial poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) and industrial poly(ethylene terephthalate) samples. .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2019

Eliminating Artifacts in Electrospray Deconvolution with a SoftMax Function

UniDec provides a rapid and robust approach to deconvolving electrospray mass spectra into their corresponding mass and charge components. However, the UniDec algorithm can produce artifacts depending on the quality and complexity of the data. Here, a SoftMax function is applied to the charge state distribution of each data point, which pushes the algorithm towards assigning each data point to one primary charge state. As shown for several data sets of increasing complexity, the SoftMax function significantly reduces deconvolution artifacts, even for data with overlapping charge states. .

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2014

Resveratrol tetramer of hopeaphenol isolated from Shorea johorensis (Dipterocarpaceae)

Hopeaphenol (1) as a resveratrol tetramer was isolated from the bark of Shorea johorensis collected from Imbak Canyon, Sabah, Malaysia. The structure of this compound was determined by the spectroscopic evidences using {sup 1}H- and {sup 13}C-NMR assigned with HSQC, HMBC, {sup 1}H−{sup 1}H COSY and {sup 1}H−{sup 1}H NOESY spectra, mass spectrum, and by comparison with reported data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Influence of relative humidity on the heterogeneous oxidation of secondary organic aerosol

Abstract. Secondary organic aerosol (SOA) is a complex mixture of hundreds of semi-volatile to extremely low-volatility organic compounds that are chemically processed in the atmosphere, including via heterogeneous oxidation by gas-phase radicals. Relative humidity (RH) has a substantial impact on particle phase, which can affect how SOA evolves in the atmosphere. In this study, SOA from dark α -pinene ozonolysis is heterogeneously aged by OH radicals in a flow tube at low and high RH. At high RH (RH = 89 %) there is substantial loss of particle volume (~60 %) at an equivalent atmospheric OH exposure of 3 weeks. In contrast, at low RH (RH = 25 %) there is little mass loss (< 20 %) at the same OH exposure. Mass spectra of the SOA particles were measured as a function of OH exposure using a vacuum ultraviolet aerosol mass spectrometer (VUV-AMS). The mass spectra observed at low RH overall exhibit minor changes with oxidation and negligible further changes above an OH exposure = 2×10 12 molecule cm -3 s suggesting limited impact of oxidation on the particle composition. In contrast, the mass spectra observed at high RH exhibit substantial and continuous changes as a function of OH exposure. Further, at high RH clusters of peaks in the mass spectra exhibit unique decay patterns, suggesting different responses of various species to oxidation. A model of heterogeneous oxidation has been developed to understand the origin of the difference in aging between the low- and high-RH experiments. Differences in diffusivity of the SOA between the low- and high-RH experiments alone can explain the difference in compositional change but cannot explain the difference in mass loss. Instead, the difference in mass loss is attributable to RH-dependent differences in the OH uptake coefficient and/or the net probability of fragmentation, with either or both larger at high RH compared to low RH. These results illustrate the important impact of relative humidity on the fate of SOA in the atmosphere.

Li, Ziyue (ORCID:0000000191017737)↗
DOE OSTI2021

MolDiscovery: learning mass spectrometry fragmentation of small molecules

Identification of small molecules is a critical task in various areas of life science. Recent advances in mass spectrometry have enabled the collection of tandem mass spectra of small molecules from hundreds of thousands of environments. To identify which molecules are present in a sample, one can search mass spectra collected from the sample against millions of molecular structures in small molecule databases. The existing approaches are based on chemistry domain knowledge, and they fail to explain many of the peaks in mass spectra of small molecules. Here, we present molDiscovery, a mass spectral database search method that improves both efficiency and accuracy of small molecule identification by learning a probabilistic model to match small molecules with their mass spectra. A search of over 8 million spectra from the Global Natural Product Social molecular networking infrastructure shows that molDiscovery correctly identify six times more unique small molecules than previous methods.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2014

Time-of-flight secondary ion mass spectrometry with transmission of energetic primary cluster ions through foil targets

We developed time-of-flight (TOF) secondary ion (SI) mass spectrometry that provides informative SI ion mass spectra without needing a sophisticated ion beam pulsing system. In the newly developed spectrometry, energetic large cluster ions with energies of the order of sub MeV or greater are used as primary ions. Because their impacts on the target surface produce high yields of SIs, the resulting SI mass spectra are informative. In addition, the start signals necessary for timing information on primary ion incidence are provided by the detection signals of particles emitted from the rear surface of foil targets upon transmission of the primary ions. This configuration allows us to obtain positive and negative TOF SI mass spectra without pulsing system, which requires precise control of the primary ions to give the spectra with good mass resolution. We also successfully applied the TOF SI mass spectrometry with energetic cluster ion impacts to the chemical structure characterization of organic thin film targets.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2019

Constraints on Cosmology and Baryonic Feedback with the Deep Lens Survey Using Galaxy–Galaxy and Galaxy–Mass Power Spectra

We present cosmological parameter measurements from the Deep Lens Survey (DLS) using galaxy–mass and galaxy–galaxy power spectra in the multipole range ℓ = 250–2000. We measure galaxy–galaxy power spectra from two lens bins centered at z ~ 0.27 and 0.54 and galaxy–mass power spectra by cross-correlating the positions of galaxies in these two lens bins with galaxy shapes in two source bins centered at z ~ 0.64 and 1.1. We marginalize over a baryonic feedback process using a single-parameter representation and a sum of neutrino masses, as well as photometric redshift and shear calibration systematic uncertainties. For a flat ΛCDM cosmology, we determine ${S}_{8}\equiv {\sigma }_{8}\sqrt{{{\rm{\Omega }}}_{m}/0.3}={0.810}_{-0.031}^{+0.039}$, in good agreement with our previous DLS cosmic shear and the Planck cosmic microwave background (CMB) measurements. Without the baryonic feedback marginalization, S 8 decreases by $\sim 0.05$ because the dark-matter-only power spectrum lacks the suppression at the highest ℓ values owing to active galactic nucleus (AGN) feedback. Together with the Planck CMB measurements, we constrain the baryonic feedback parameter to ${A}_{\mathrm{baryon}}={1.07}_{-0.39}^{+0.31}$, which suggests an interesting possibility that the actual AGN feedback might be stronger than the recipe used in the OverWhelmingly Large cosmological hydrodynamical Simulations. The interpretation is limited by the validity of the baryonic feedback simulation and the one-parameter representation of the effect.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2019

Mass Spectrometry of a Xylitol Molecule

The technique and results of a mass spectrometric study on the yield of positive ions formed upon ionization of xylitol molecules by electron impact are discussed. The mass spectra of xylitol are studied in the range of mass numbers of 10–160 Da and in the range of bombarding electrons energies of 5–80 eV. Based on the analysis of the measured mass spectra, a scheme of xylitol fragmentation is proposed, which contains the most probable channels of formation of ion-fragments upon electron impact, when the energy of the incident electrons significantly exceeds the ionization potential of the molecule. The appearance energies of ionized fragments of xylitol are determined for the first time from the energy dependences of the effective cross-section formation of the ions upon electron impact. The dynamics of ionized fragment formation is studied in the temperature range of the initial substance evaporation of 340–410 K. The behavior of the temperature dependence indicates that the formation processes of water and oxonium cations compete with each other.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2019

Gas-Phase Chemistry in the GC Orbitrap Mass Spectrometer

Gas-phase reactions of temporally stored ions play a significant role in trapped ion mass spectrometry. Especially highly labile ion species generated through electron ionization (EI) are prone to undergo gas-phase reactions after relaxation to a low vibrational state. Here, we show that in the C-Trap of the Q Exactive GC Orbitrap mass spectrometer, gaseous water reacts with radical cations of various compound classes. High-resolution accurate mass spectrometry of the resulting ions provides a key to the mechanistic understanding of the chemistry of high energetic species generated during EI. We systematically addressed water adduct formation by use of H{sub 2}O and D{sub 2}{sup 18}O in the C-Trap. Mass spectra of halogen cyanides XCN (X=Cl, Br, I) showed the formation of HXCN{sup +} species, indicating hydrogen atomic transfer reactions. Relative ratios of HXCN{sup +}/XCN{sup +•} increased as the electronegativity of the halide increased. The common internal calibrant perfluorotributylamine forms oxygenated products from water reactive fragment ions. These can be explained by the addition of water to an initial cation followed by elimination of two HF molecules. This addition/elimination chemistry can also explain [M+2]{sup +} and [M+3]{sup +} ions that commonly occur in mass spectra of silylated analytes. High-resolution accurate mass spectra of trimethylsilyl (TMS) derivatives revealed these as [M−CH{sub 3}{sup •}+H{sub 2}O]{sup +} and [M−CH{sub 4}+H{sub 2}O]{sup •+}, respectively. This study explains common fragment ions in ion trap mass spectrometry. It also opens up perspectives for the systematic mechanistic and kinetic investigation of high-energy ion reactivity. .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2018

Liquid Extraction Surface Analysis (LESA) Electron-Induced Dissociation and Collision-Induced Dissociation Mass Spectrometry of Small Molecule Drug Compounds

Here, we present liquid extraction surface analysis (LESA) coupled with electron-induced dissociation (EID) mass spectrometry in a Fourier-transform ion cyclotron resonance mass spectrometer for the analysis of small organic pharmaceutical compounds directly from dosed tissue. First, the direct infusion electrospray ionisation EID and collision-induced dissociation (CID) behaviour of erlotinib, moxifloxacin, clozapine and olanzapine standards were compared. EID mass spectra were also compared with experimental or reference electron impact ionisation mass spectra. The results show that (with the exception of erlotinib) EID and CID result in complementary fragment ions. Subsequently, we performed LESA EID MS/MS and LESA CID MS/MS on singly charged ions of moxifloxacin and erlotinib extracted from a thin tissue section of rat kidney from a cassette-dosed animal. Both techniques provided structural information, with the majority of peaks observed for the drug standards also observed for the tissue-extracted species. Overall, these results demonstrate the feasibility of LESA EID MS/MS of drug compounds from dosed tissue and extend the number of molecular structures for which EID behaviour has been determined. .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Ion distribution measurements to probe target and plasma processes in electronegative magnetron discharges. II. Positive ions

Spectra of the ion mass and energy distributions of positive ions in reactive (Ar/O{sub 2}) and nonreactive (Ar) dc magnetron sputtering discharges have been investigated by energy-resolved mass spectrometry. The results of three sputter target materials, i.e., Cu, In, and W are compared to each other. Besides the main gas constituents, mass spectra reveal a variety of molecular ions which are dependent on the target material. In reactive mode, ArO{sup +} is always observed in Ar/O{sub 2} but molecules containing Ar and the metal were exclusively found for the Cu target. The occurrence of the different ions is explained in the context of their bond strengths obtained from density functional theory calculations. The energy spectra generally contain the known low-energy peak corresponding to the plasma potential. Differently extended high-energy tails due to sputtered material were observed for the different targets. Besides these, high-energetic ions were detected with up to several 100 eV. Their energies are significantly different for Ar{sup +} and O{sup +} with Ar{sup +} strongly depending on the target material. The spectra are discussed together with results from transport of ions in matter (TRIM) calculation to elucidate the origin of these energetic ions.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Submicron particle mass concentrations and sources in the Amazonian wet season (AMAZE-08)

Real-time mass spectra of non-refractory component of submicron aerosol particles were recorded in a tropical rainforest in the central Amazon basin during the wet season of 2008, as a part of the Amazonian Aerosol Characterization Experiment (AMAZE-08). Organic components accounted on average for more than 80% of the non-refractory submicron particle mass concentrations during the period of measurements. Ammonium was present in sufficient quantities to halfway neutralize sulfate. In this acidic, isoprene-dominated, low-NOx environment the high-resolution mass spectra as well as mass closures with ion chromatography measurements did not provide evidence for significant contributions of organosulfate species, at least at concentrations above uncertainty levels. Positive-matrix factorization of the time series of particle mass spectra identified four statistical factors to account for the variance of the signal intensities of the organic constituents: a factor HOA having a hydrocarbon-like signature and identified as regional emissions of primary organic material, a factor OOA-1 associated with fresh production of secondary organic material by a mechanism of BVOC oxidation followed by gas-to-particle conversion, a factor OOA-2 consistent with reactive uptake of isoprene oxidation products, especially epoxydiols by acidic particles, and a factor OOA-3 associated with long range transport and atmospheric aging. The OOA-1, -2, and -3 factors had progressively more oxidized signatures. Diameter-resolved mass spectral markers also suggested enhanced reactive uptake of isoprene oxidation products to the accumulation mode for the OOA-2 factor, and such size partitioning can be indicative of in-cloud process. The campaign-average factor loadings were in a ratio of 1.1:1.0 for the OOA-1 compared to the OOA-2 pathway, suggesting the comparable importance of gas-phase compared to particle-phase (including cloud waters) production pathways of secondary organic material during the study period.

Chen, Q.↗
DOE OSTI2011

Cs atoms on helium nanodroplets and the immersion of Cs{sup +} into the nanodroplet

We report the non-desorption of cesium (Cs) atoms on the surface of helium nanodroplets (He{sub N}) in their 6{sup 2}P{sub 1/2} ({sup 2}{Pi}{sub 1/2}) state upon photo-excitation as well as the immersion of Cs{sup +} into the He{sub N} upon photo-ionization via the 6{sup 2}P{sub 1/2} ({sup 2}{Pi}{sub 1/2}) state. Cesium atoms on the surface of helium nanodroplets are excited with a laser to the 6{sup 2}P states. We compare laser-induced fluorescence (LIF) spectra with a desorption-sensitive method (Langmuir-Taylor detection) for different excitation energies. Dispersed fluorescence spectra show a broadening of the emission spectrum only when Cs-He{sub N} is excited with photon energies close to the atomic D{sub 1}-line, which implies an attractive character of the excited state system (Cs*-He{sub N}) potential energy curve. The experimental data are compared with a calculation of the potential energy curves of the Cs atom as a function of its distance R from the center of the He{sub N} in a pseudo-diatomic model. Calculated Franck-Condon factors for emission from the 6{sup 2}P{sub 1/2} ({sup 2}{Pi}{sub 1/2}) to the 6{sup 2}S{sub 1/2} ({sup 2}{Sigma}{sub 1/2}) state help to explain the experimental data. The stability of the Cs*-He{sub N} system allows to form Cs{sup +} snowballs in the He{sub N}, where we use the non-desorbing 6{sup 2}P{sub 1/2} ({sup 2}{Pi}{sub 1/2}) state as a springboard for ionization in a two-step ionization scheme. Subsequent immersion of positively charged Cs ions is observed in time-of-flight mass spectra, where masses up to several thousand amu were monitored. Only ionization via the 6{sup 2}P{sub 1/2} ({sup 2}{Pi}{sub 1/2}) state gives rise to a very high yield of immersed Cs{sup +} in contrast to an ionization scheme via the 6{sup 2}P{sub 3/2} ({sup 2}{Pi}{sub 3/2}) state. When resonant two-photon ionization is applied to cesium dimers on He droplets, Cs{sub 2}{sup +}-He{sub N} aggregates are observed in time-of-flight mass spectra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Photoinduced Charge Transfer versus Fragmentation Pathways in Lanthanum Cyclopentadienyl Complexes

This study compares two competing pathways of photoexcitations in gas-phase metal–organic complexes: first, a sequence of phonon-assisted electronic transitions leading to dissipation of the energy of photoexcitations and, second, a sequence of light-driven electronic transitions leading to photolysis. Phonon-assisted charge carrier dynamics is investigated by combination of the density matrix formalism and on-the-fly nonadiabatic couplings. Light-driven fragmentation is modeled by a time-dependent excited-state molecular-dynamics (TDESMD) algorithm based on Rabi theory and principles similar to the trajectory surface hopping approximation. Numerical results indicate that, under the medium intensity of the laser field, light-driven electronic transitions are more probable than phonon-assisted ones. The formation of multiple products is observed in TDESMD trajectories. Simulated mass spectra are extracted from TDESMD simulations and compared to experimental photoionization time-of-flight (PI-TOF) mass spectra. It is found that several features in the experimental mass spectra are reproduced by the simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2022

Compositional Measurements of Saturn's Upper Atmosphere and Rings From Cassini INMS: An Extended Analysis of Measurements From Cassini's Grand Finale Orbits

The Cassini spacecraft's final orbits sampled Saturn's atmosphere and returned surprisingly complex mass spectra from the Ion and Neutral Mass Spectrometer (INMS). Signal returned from the instrument included native Saturn species, as expected, as well as a significant amount of signal attributed to vaporized ices and higher mass organics believed to be owing into Saturn's atmosphere from the rings. In this paper, we present an in-depth compositional analysis of the mass spectra returned from Cassini's last few orbits. We use a mass spectral deconvolution algorithm designed specifically to handle the complexities involved with unit resolution spaceflight mass spectrometry data to determine the relative abundance of species detected in the observations. We calculate the downward external flux and mass deposition rates of ring volatile species into Saturn's atmosphere and conclude that during these observations ring material was being deposited into Saturn's equatorial region at a rate on the order of 10(exp 4) kg/s.

Saturn↗
NASA NTRS2022

Compositional Measurements of Saturn's Upper Atmosphere and Rings From Cassini INMS: An Extended Analysis of Measurements From Cassini's Grand Finale Orbits

The Cassini spacecraft's final orbits sampled Saturn's atmosphere and returned surprisingly complex mass spectra from the Ion and Neutral Mass Spectrometer (INMS). Signal returned from the instrument included native Saturn species, as expected, as well as a significant amount of signal attributed to vaporized ices and higher mass organics believed to be flowing into Saturn's atmosphere from the rings. In this paper, we present an in-depth compositional analysis of the mass spectra returned from Cassini's last few orbits. We use a mass spectral deconvolution algorithm designed specifically to handle the complexities involved with unit resolution spaceflight mass spectrometry data to determine the relative abundance of species detected in the observations. We calculate the downward external flux and mass deposition rates of ring volatile species into Saturn's atmosphere and conclude that during these observations ring material was being deposited into Saturn's equatorial region at a rate on the order of 10(exp 4) kg/s.

Saturn↗
DOE OSTI2021

Development of an inexpensive matrix-assisted laser desorption—time of flight mass spectrometry method for the identification of endophytes and rhizobacteria cultured from the microbiome associated with maize

Many endophytes and rhizobacteria associated with plants support the growth and health of their hosts. The vast majority of these potentially beneficial bacteria have yet to be characterized, in part because of the cost of identifying bacterial isolates. Matrix-assisted laser desorption-time of flight (MALDI-TOF) has enabled culturomic studies of host-associated microbiomes but analysis of mass spectra generated from plant-associated bacteria requires optimization. In this study, we aligned mass spectra generated from endophytes and rhizobacteria isolated from heritage and sweet varieties of Zea mays. Multiple iterations of alignment attempts identified a set of parameters that sorted 114 isolates into 60 coherent MALDI-TOF taxonomic units (MTUs). These MTUs corresponded to strains with practically identical (>99%) 16S rRNA gene sequences. Mass spectra were used to train a machine learning algorithm that classified 100% of the isolates into 60 MTUs. These MTUs provided >70% coverage of aerobic, heterotrophic bacteria readily cultured with nutrient rich media from the maize microbiome and allowed prediction of the total diversity recoverable with that particular cultivation method. Acidovorax sp., Pseudomonas sp. and Cellulosimicrobium sp. dominated the library generated from the rhizoplane. Relative to the sweet variety, the heritage variety contained a high number of MTUs. The ability to detect these differences in libraries, suggests a rapid and inexpensive method of describing the diversity of bacteria cultured from the endosphere and rhizosphere of maize.

dereplication↗