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Grubisic, Andrej

Publications and source records attributed to Grubisic, Andrej.

9 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS2019

Investigating the Effects of Gamma Radiation on Selected Chemicals for Use in Biosignature Detection Instruments on the Surface of Jupiter's Moon Europa

Jupiter's moon Europa is a prime target for the search for potential signs of life in the solar system. The Europa Lander Science Definition Team Report outlined investigations and measurement requirements on a future Europa Lander and has led us to consider application of powerful techniques such as pyrolysis and derivatization gas chromatography mass spectrometry (GC-MS) and laser desorption mass spectrometry (LD-MS) to elucidate the organic composition of near-surface ice and minerals. Definitive identification of chemical biosignatures using such techniques is strongly enabled by the use of various chemicals, such as perfluorotributylamine (PFTBA) for the MS calibration, α-cyano-hydroxycinnamic acid (CHCA) for matrix-assisted laser desorption and ionization (MALDI) and N,N-dimethylformamide dimethyl acetal (DMF-DMA), N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA) and tetramethylammonium hydroxide (TMAH) for wet chemistry GC-MS protocols. The jovian radiation environment is known to represent a uniquely challenging risk to mission performance and lifetime, principally due to high radiation levels. To assess the potential ionizing radiation damage to these important chemicals, we tested their effectiveness following gamma radiation exposure doses up to the anticipated Europa Lander rating requirement of 300 krad(Si). The chemicals were sealed in glass ampules under vacuum (<10 mTorr), to reduce trapped oxygen gas, as the oxidation by O2 may be enhanced in the presence of radiation. We report that all five chemicals exposed to total ionizing doses of 0, 150 and 300 krad(Si) maintained their full effectiveness, and no significant degradation was observed.

Radiation↗
NASA NTRS2019

Future Planetary Instrument Capabilities Made Possible by Micro- and Nanotechnology

A number of new instrument capabilities are currently in maturation for future in situ use on planetary science missions. Moving beyond the impressive in situ instrumentation already operating in planetary environments beyond Earth will enable the next step in scientific discovery. The approach for developing beyond current instrumentation requires a careful assessment of science-driven capability advancement. To this end, two examples of instrument technology development efforts that are leading to new and important analytical capabilities for in situ planetary science will be discussed: (1) an instrument prototype enabling the interface between liquid separation techniques and laser desorption/ionization mass spectrometry and (2) an addressable excitation source enabling miniaturized electron probe microanalysis for elemental mapping of light and heavy elements.

Getty, Stephanie A.↗
NASA NTRS2018

A Compact Two-Step Laser Time-Of-Flight Mass Spectrometer for In Situ Analysis of Planetary Surfaces

Two-step laser mass spectrometry (L2MS) has proved to be a powerful tool for the analysis of aromatic organics in icy planetary simulants, meteorites, asphaltenes on Earth, and returned cometary particles from the Stardust mission. L2MS employs two lasers to separate the desorption and ionization processes of laser desorption ionization into distinct steps. In the first step, an infrared laser desorbs neutrals from a solid sample surface; in the second step, an ultraviolet laser forms molecular ions within the neutral plume through a resonance-enhanced process to minimize fragment at ion of complex species. We have recently demonstrated that the L2MS technique is compatible with a compact TOF-MS that could form the center piece of a future in situ landed planetary mission emphasizing surface chemistry or astrobiology. The increased sensitivity and selectivity offered by this technique has been demonstrated in analyses of various planetary analog mixtures and meteorite powders, and representative results of these analyses will be presented.

Getty, Stephanie A.↗
NASA NTRS2018

Probing the Composition of Primitive Solar System Materials with a Compact Laser Mass Spectrometer

To contribute to and complement our understanding of the processes governing the formation,distribution, and evolution of primitive materials throughout the solar system, it will be critical toform connections between broad remote sensing spectroscopic surveys, laboratorymeasurements of analogs and samples delivered to Earth, and in situ measurements of thesurface composition on future primitive body missions. Recently, a laboratory prototypeemploying resonance two-step laser mass spectrometry [Getty et al., 2012] has been coupledto a cryogenic sample stage to enable measurements of analog samples that are relevant tothese fundamental questions. Analyses of mineral-aromatic mixtures and meteorite powderswill be presented. Our goals are twofold: (1) to conduct laboratory studies on solar systemanalog, meteoritic, and potentially returned samples to elucidate composition, and (2) toprovide a compact but capable analytical instrument for discovery-driven in situ interrogationof surface chemistry on a future mission, such as to a Trojan asteroid, comet, or icy moon.

Getty, Stephanie A.↗
NASA NTRS2018

Numerical Investigation of Ion Transport in the MOMA Ion Mass Spectrometer

The Mars Organic Molecule Analyzer (MOMA) is a miniature ion trap mass spectrometer designed for the upcoming ExoMars Rover mission. The spectrometer uses laser desorption to ionize a Martian soil sample within an instrument internal clean zone maintained at ambient Martian pressure. A high-speed aperture valve transiently opens to allow ionized constituents, along with the ambient gas, to enter a vacuum cavity containing a linear ion trap mass spectrometer. The ambient clean zone and the vacuum cavity are connected via a few centimeter long aperture valve ion guide tube. In this paper, we present results from a recently completed numerical investigation of ion transport from the ion source across the ion guide. Specifically, we focus on collisional coupling between ions and the neutral molecules flowing into the vacuum cavity. The simulation domain contains the ambient region, and we consider the variation in ion conductance with ambient pressure. We also analyze the impact of a fixed potential bias applied to the aperture valve. Simulations are performed with a two-dimensional axisymmetric PIC / DSMC code Starfish. Numerical results are compared to experimental data.

Breida, Lubos↗
NASA NTRS2018

Polarization-Controlled Directional Multiphoton Photoemission from Hot Spots on Single Au Nanoshells

Directional photoemission from single Au nanoshells is demonstrated in the low-intensity, multiphoton regime. Thisdirectionality is shown to be due to the plasmonic excitation of highly photoemissive, nanometer scale surface regions, which are characterized by correlated momentum mapping, scanning electron microscopy (SEM), and laser polarization-dependence studies. Furthermore, the photoelectron flux from a single nanoshell can be systematically rotated by over 90° in momentum space simply by polarization-controlled coupling to different hot spots. Photoelectrondistributions are directly characterized in momentum space via velocity map imaging (VMI) of the two-dimensional transverse (px, py) momentum components for single nanoshells. For the majority of nanoshells studied, the photoemission is directionally orthogonal to the laser polarization, which implicates nanoscale crevice-shaped "hotspots" clearly observed in the correlated SEM/VMI studies, with the near-field plasmonic nature of these crevices clarified further via finite-element simulations. These results rationalize the large photoemission enhancements observed in previous Au nanoshell studies, but more importantly provide a novel experimental access to directionally tunable electron emission from nanoscale sources. The ability to control photoemission/photocurrent angular distributions at the nanoscale with only modest optical fields indicates a new parameter for optimizing nanoplasmonic system performance and suggests new plasmonic applications such as ultrafast, polarization-controlled photoelectric/photovoltaic switches.

Pettine, Jacob↗
NASA NTRS2017

Molecular Analyzer for Complex Refractory Organic-Rich Surfaces (MACROS)

The Molecular Analyzer for Complex Refractory Organic-rich Surfaces, MACROS, is a novel instrument package being developed at NASA Goddard Space Flight Center. MACROS enables the in situ characterization of a sample's composition by coupling two powerful techniques into one compact instrument package: (1) laser desorption/ionization time-of-flight mass spectrometry (LDMS) for broad detection of inorganic mineral composition and non-volatile organics, and (2) liquid-phase extraction methods to gently isolate the soluble organic and inorganic fraction of a planetary powder for enrichment and detailed analysis by liquid chromatographic separation coupled to LDMS. The LDMS is capable of positive and negative ion detection, precision mass selection, and fragment analysis. Two modes are included for LDMS: single laser LDMS as the broad survey mode and two step laser mass spectrometry (L2MS). The liquid-phase extraction will be done in a newly designed extraction module (EM) prototype, providing selectivity in the analysis of a complex sample. For the sample collection, a diamond drill front end will be used to collect rock/icy powder. With all these components and capabilities together, MACROS offers a versatile analytical instrument for a mission targeting an icy moon, carbonaceous asteroid, or comet, to fully characterize the surface composition and advance our understanding of the chemical inventory present on that body.

Getty, Stephanie A.↗
NASA NTRS2017

Multi-Wavelength Laser Transmitter for the Two-Step Laser Time-of-Flight Mass Spectrometer

Missions to diverse Outer Solar System bodies will require investigations that can detect a wide range of organics in complex mixtures, determine the structure of selected molecules, and provide powerful insights into their origin and evolution. Previous studies from remote spectroscopy of the Outer Solar System showed a diverse population of macromolecular species that are likely to include aromatic and conjugated hydrocarbons with varying degrees of methylation and nitrile incorporation. In situ exploration of Titan's upper atmosphere via mass and plasma spectrometry has revealed a complex mixture of organics. Similar material is expected on the Ice Giants, their moons, and other Outer Solar System bodies, where it may subsequently be deposited onto surface ices. It is evident that the detection of organics on other planetary surfaces provides insight into the chemical and geological evolution of a Solar System body of interest and can inform our understanding of its potential habitability. We have developed a prototype two-step laser desorption/ionization time-of-flight mass spectrometer (L2MS) instrument by exploiting the resonance-enhanced desorption of analyte. We have successfully demonstrated the ability of the L2MS to detect hydrocarbons in organically-doped analog minerals, including cryogenic Ocean World-relevant ices and mixtures. The L2MS instrument operates by generating a neutral plume of desorbed analyte with an IR desorption laser pulse, followed at a delay by a ultraviolet (UV) laser pulse, ionizing the plume. Desorption of the analyte, including trace organic species, may be enhanced by selecting the wavelength of the IR desorption laser to coincide with IR absorption features associated with vibration transitions of minerals or organic functional groups. In this effort, a preliminary laser developed for the instrument uses a breadboard mid-infrared (MIR) desorption laser operating at a discrete 3.475 μm wavelength, and a breadboard UV ionization laser operating at a wavelength of 266 nm. The MIR wavelength was selected to overlap the C-H stretch vibrational transition of certain aromatic hydrocarbons, and the UV wavelength provides additional selectivity to aromatic species via UV resonance-enhanced multiphoton ionization effects. The use of distinct laser wavelengths allows efficient coupling to the vibrational and electronic spectra of the analyte in independent desorption and ionization steps, mitigating excess energy that can lead to fragmentation during the ionization process and leading to selectivity that can aid in data interpretation.

Yu, Anthony W.↗