Engineering topics

Zare, Richard N.

Publications and source records attributed to Zare, Richard N..

At least 19 records

NASA NTRS2005

Investigation of the Reactions and Distribution of Polycyclic Aromatic Hydrocarbons and Fullerenes in Extraterrestrial Material

The work funded by this research grant includes four specific projects: (1) Mapping the spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. (2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe laser-desorption laser-ionization mass spectrometry ( pL2MS) and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. (3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. (4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames.

Zare, Richard N.↗

NASA NTRS2003

Understanding Organics in Meteorites and the Pre-Biotic Environment

(1) Refinement of the analytic capabilities of our experiment via characterization of molecule-specific response and the effects upon analysis of the type of sample under investigation; (2) Measurement of polycyclic aromatic hydrocarbons (PAHs) with high sensitivity and spatial resolution within extraterrestrial samples; (3) Investigation of the interstellar reactions of PAHs via the analysis of species formed in systems modeling dust grains and ices; (4) Investigations into the potential role of PAHs in prebiotic and early biotic chemistry via photoreactions of PAHs under simulated prebiotic Earth conditions. To meet these objectives, we use microprobe laser-desorption, laser-ionization mass spectrometry (MuL(exp 2)MS), which is a sensitive, selective, and spatially resolved technique for detection of aromatic compounds. Appendix A presents a description of the MuL(exp 2)MS technique. The initial grant proposal was for a three-year funding period, while the award was given for a one-year interim period. Because of this change in time period, emphasis was shifted from the first research goal, which was more development-oriented, in order to focus more on the other analysis-oriented goals. The progress made on each of the four research areas is given below.

Zare, Richard N.↗

NASA NTRS2002

Side Group Addition to the PAH Coronene by UV Photolysis in Cosmic Ice Analogs

Ultraviolet photolysis of various ice mixtures at low temperature and pressure caused the addition of amino (-NH2), methyl (-CH3), methoxy (-OCH3), and cyano (-CN) functional groups to the polycyclic aromatic hydrocarbon (PAH) coronene (C22H12). The implications of these results for interstellar and meteoritic chemistry are discussed. Previously only simple PAH photo-oxidation had been reported. This work represents the first experimental evidence that ice photochemistry may have contributed to aromatics bearing carbon and nitrogen containing side groups that are detected in primitive meteorites and interplanetary dust particles. Furthermore, these results suggest a wider range of modified PAHs should be expected in interstellar lees and materials predating solar system formation.

Bernstein, Max P.↗

NASA NTRS2001

Organic Synthesis in Simulated Interstellar Ice Analogs

Comets and carbonaceous micrometeorites may have been significant sources of organic compounds on the early Earth. Ices on grains in interstellar dense molecular clouds contain a variety of simple molecules as well as aromatic molecules of various sizes. While in these clouds the icy grains are processed by ultraviolet light and cosmic radiation which produces more complex organic molecules. We have run laboratory simulations to identify the types of molecules which could have been generated photolytically in pre-cometary ices. Experiments were conducted by forming various realistic interstellar mixed-molecular ices with and without polycyclic aromatic hydrocarbons (PAHs) at approx. 10 K under high vacuum irradiated with UV light from a hydrogen plasma lamp. The residue that remained after warming to room temperature was analyzed by HPLC, and by laser desorption mass spectrometry. The residue contains several classes of compounds which may be of prebiotic significance.

Dworkin, Jason P.↗

NASA NTRS2001

Organic Synthesis in Simulated Interstellar Ice Analogs

Comets and carbonaceous micrometeorites may have been significant sources of organic compounds on the early Earth. Ices on grains in interstellar dense molecular clouds contain a variety of simple molecules as well as aromatic molecules of various sizes. While in these clouds the icy grains are processed by ultraviolet light and cosmic radiation which produces more complex organic molecules. ID We have run laboratory simulations to identify the types of molecules which could have been generated photolytically in pre-cometary ices. Experiments were conducted by forming various realistic interstellar mixed-molecular ices with and without polycyclic aromatic hydrocarbons (PAHs) at approx. 10 K under high vacuum irradiated with LTV light from a hydrogen plasma lamp: The residue that remained after warming to room temperature was analyzed by HPLC, and by laser desorption mass spectrometry. The residue contains several classes of compounds which may be of prebiotic significance.

Dworkin, Jason P.↗

NASA NTRS2001

Chemical and Isotopic Analysis of Trace Organic Matter on Meteorites and Interstellar Dust Using a Laser Microprobe Instrument

Polycyclic Aromatic Hydrocarbons (PAHs) are of considerable interest today because they are ubiquitous on Earth and in the interstellar medium (ISM). In fact, about 20% of cosmic carbon in the galaxy is estimated to be in the form of PAHs. Investigation of these species has obvious uses for determining the cosmochemistry of the solar system. Work in this laboratory has focused on four main areas: 1) Mapping the spatial distribution of PAHs in a variety of meteoritic samples and comparing this distribution with mineralogical features of the meteorite to determine whether a correlation exists between the two. 2) Developing a method for detection of fullerenes in extraterrestrial samples using microprobe Laser Desorption Ionization Mass Spectroscopy and utilizing this technique to investigate fullerene presence, while exploring the possibility of spatially mapping the fullerene distribution in these samples through in situ detection. 3) Investigating a possible formation pathway for meteoritic and ancient terrestrial kerogen involving the photochemical reactions of PAHs with alkanes under prebiotic and astrophysically relevant conditions. 4) Studying reaction pathways and identifying the photoproducts generated during the photochemical evolution of PAH-containing interstellar ice analogs as part of an ongoing collaboration with researchers at the Astrochemistry Lab at NASA Ames. All areas involve elucidation of the solar system formation and chemistry using microprobe Laser Desorption Laser Ionization Mass Spectrometry. A brief description of microprobe Laser Desorption Ionization Mass Spectroscopy, which allows selective investigation of subattomole levels of organic species on the surface of a sample at 10-40 micrometer spatial resolution, is given.

Zare, Richard N.↗

NASA NTRS2000

Formation of Prebiotic Molecules in Interstellar and Cometary Ices

We report here on our lab studies of ice photochemistry of large organic molecules under cometary conditions. We focus on polycyclic aromatic hydrocarbons (PAHs), their photoproducts, and their similarities to molecules seen in living systems today. We note that these kinds of compounds are seen in meteorites and we propose an explanation for both their formation and their observed deuterium enrichments.

Bernstein, Max P.↗

NASA NTRS1999

Search for Unique Organic Biomarkers in ALH84001

Four goals were outlined for this project. These were: [1] to reproduce the measurement of polycyclic aromatic hydrocarbons (PAHS) in ALH84001 with both a higher spatial resolution and sensitivity than has been previously reported; [2] to extend such measurements to include other members of the Martian SNC (Shergotties, Nahklites, and Chassigny) meteorite clan, in particular the Antarctic Martian meteorite EETA79001; [3] to address issues of potential organic contamination, because at present very little is known about the effect of terrestrial weathering in the Antarctic environment as it pertains to perturbing an indigenous organic distribution within a meteoritic matrix; and [4] to diversify the range of organic compounds studied to include species that can serve as unique biological markers - "molecular fossils" - derived from once living organisms. In order to achieve this, three specific goals were outlined for the funding period 06/01/97 to 02/28/98. They were: [1] to investigate the effects of terrestrial weathering and organic contamination of meteoritic samples collected from Antarctica; [2] to reproduce and extend upon the measurements of PAHs in ALH84001 with the aim of establishing or refuting the indigeneity of these species; and [3] to extend the analysis of organic compounds in ALH84001 and EETA79001 to address compounds that are considered to be more biologically relevant than PAHS. All three were successfully accomplished, as detailed in the previous performance report. In brief, however, the results achieved were to establish that the PAHs found in ALH84001 were indigenous and not due to contamination, and to determine that a novel and sensitive technique in meteoritic work, capillary zone electrophoresis (CE), could indeed detect amino acids, a potential class of biomarker.

Zare, Richard N.↗

NASA NTRS1999

Synthesis of Large Molecules in Cometary Ice Analogs: Physical Properties Related to Self-Assembly Processes

The combination of realistic laboratory simulations and infrared observations have revolutionized our understanding of interstellar dust and ice-the main component of comets. Since comets and carbonaceous micrometeorites may have been important sources of volatiles and carbon compounds on the early Earth, their organic composition may be related to the origin of life. Ices on grains in molecular clouds contain a variety of simple molecules. The D/H ratios of the comets Hale-Bopp and Hyakutake are consistent with a primarily interstellar ice mixture. Within the cloud and especially in the presolar nebula through the early solar system, these icy grains would have been photoprocessed by the ultraviolet producing more complex species such as hexamethylenetetramine, polyoxymethylenes, and simple keones. We reported at the 1999 Bioastronomy meeting laboratory simulations studied to identify the types of molecules which could have been generated in pre-cometary ices. Experiments were conducted by forming a realistic interstellar mixed-molecular ice (H2O, CH3OH, NH3 and CO) at approximately 10 K under high vacuum irradiated with UV light from a hydrogen plasma lamp. The gas mixture was typically 100:50:1:1, however when different ratios were used material with similar characteristics was still produced. The residue that remained after warming to room temperature was analyzed by HPLC, and by several mass spectrometric methods. This material contains a rich mixture of complex compounds with mass spectral profiles resembling those found in IDPs and meteorites. Surface tension measurements show that an amphiphilic component is also present. These species do not appear in various controls or in unphotolyzed samples. Residues from the simulations were also dispersed in aqueous media for microscopy. The organic material forms 10-40 gm diameter droplets that fluoresce at 300-450 nm under UV excitation. These droplets have a morphology and internal structure which appear strikingly similar to those produced by extracts of the Murchison meteorite. Together, these results suggest a link between organic material photochemically synthesized on the cold grains in dense, interstellar molecular clouds and compounds that may have contributed to the organic inventory of the primitive Earth. For example, the amphiphilic properties of such compounds permit self-assembly into the membranous boundary structures that required for the first forms of cellular life.

Dworkin, Jason P.↗

NASA NTRS1998

Analyses at High Spatial Resolution of Organic Molecules in Extraterrestrial Samples: Two-Step Laser Mass Spectrometry: Search for Polycyclic Aromatic Hydrocarbons in Antarctic Meteorite and Micrometeorite Samples

Perhaps the best way to summarize the past three-year grant period is to cite the publications and present a brief synopsis of each: 1. "Indigenous Polycyclic Aromatic Hydrocarbon Molecules in Circumstellar Graphite Grains." Bulk C-12/C-13 isotope ratios observed in some graphite grains extracted from primitive meteorites point strongly to a circumstellar origin. By applying our technique of microprobe two-step laser desorption laser ionization mass spectrometry ((mu)L(sup 2)MS) to individual circumstellar graphite grains we have measured the C-12/C-13 isotope ratio of various polycyclic aromatic hydrocarbons (PAHS) found in these grains. 2. "Deuterium Enrichments in Cluster IDPS," Large enrichments in the D/H isotope ratios in IDPs likely arise from the preservation of presolar molecules. 3. "Evidence for thermalization of surface-disorder molecules at heating rates of 10(exp 8) K/s". A careful study of the ((mu)L(sup 2)MS) of aniline-d(sub 7) from a single-crystal surface (0001) of sapphire (al2O3) shows that all measured properties are consistent with a thermal mechanism for desorption. 4. "Search for past life on Mars; possible relic biogenic activity in Martian meteorite ALH 84001. The authors examined the Martian meteorite ALH 84001 and found several lines of evidence compatible with existence of past primitive (single-cell) life on early Mars. 5. "Microprobe two-step laser mass spectrometry as an analytical tool for meteorite samples". THis paper presents a comprehensive review of (mu)L(sup 2)MS and how this technique can be applied to meteoritic samples. 6. "Indigenous polycyclic aromatic hydrocarbons in circumstellar graphite grains from primitive meteorites". The C-12/C-13 isotope ratios were measured for PAHs in a total of 89 spherical graphite grains. 7. "Observation of indigenous polycyclic aromatic hydrocarbons in "Giant" carbonaceous antarctic micrometeorites." The (mu)L(sup 2)MS method was used to establish the nature and distribution of PAHs in fragments of fifteen (approx. 200 microns) carbonaceous antarctic micrometeorites (AMMs). 8. "Evidence for the extraterrestrial origin of polycyclic aromatic hydrocarbons in the Martian meteorite ALH 84001" We have undertaken additional contamination studies of ALH 84001.

Zare, Richard N.↗

NASA NTRS1998

Deuterium Enrichment of PAHs by VUV Irradiation of Interstellar Ices

Laboratory results demonstrate that polycyclic aromatic hydrocarbons (PAHs) rapidly exchange their hydrogen atoms with those of nearby molecules when they are frozen into low-temperature ices and exposed to vacuum ultraviolet radiation. As a result, PAHs quickly become deuterium-enriched when VUV irradiated in D-containing ices. This mechanism has important consequences for several astrophysical issues owing to the ubiquitous nature of PAHs in the interstellar medium. For example, this process may explain the deuterium enrichments found in PAHs in meteorites and interplanetary dust particles. These results also provide general predictions about the molecular siting of the deuterium on aromatic materials in meteorites if this process produced a significant fraction of their D-enrichment.

Bernstein, Max P.↗

NASA NTRS1996

Search for Past Life on Mars: Possible Relict Biogenic Activity in Martian Meteorite ALH84001

Fresh fracture surfaces of the martian meteorite ALH84001 contain abundant polycyclic aromatic hydrocarbons (PAHs). These fresh fracture surfaces also display carbonate globules. Contamination studies suggest the PAHs are indigenous to the meteorite. High resolution scanning and transmission electron microscopy study of surface textures and internal structures of selected carbonate globules show that the globules contain fine-grained, secondary phases of single-domain magnetite and Fe-monosulfides. The carbonate globules are similar in texture and size to some terrestrial bacterially induced carbonate precipitates. Although inorganic formation is possible, formation of the globules by biogenic processes could explain many of the observed features including the PAHs. The PAHs, the carbonate globules, and their associated secondary mineral phases and textures could thus be fossil remains of a past martian biota.

McKay, David S.↗

NASA NTRS1992

State-to-state rates for the D + H2(v = 1, j = 1) yield HD(v-prime, j-prime) + H reaction - Predictions and measurements

A fully quantal wavepacket approach to reactive scattering in which the best available H3 potential energy surface was used enabled a comparison with experimentally determined rates for the D + H2(v = 1, j = 1) yield HD(v-prime = 0, 1, 2; j-prime) + H reaction at significantly higher total energies (1.4 to 2.25 electron volts) than previously possible. The theoretical results are obtained over a sufficient range of conditions that a detailed simulation of the experiment was possible, thus making this a definitive comparison of experiment and theory. Good to excellent agreement is found for the vibrational branching ratios and for the rotational distributions within each product vibrational level. However, the calculated rotational distributions are slightly hotter than the experimentally measured ones.

Neuhauser, Daniel↗

NASA NTRS1991

Rotational and vibrational effects in the E 1Sigma(+)g-X 1Sigma(+)g two-photon transitions of H2, HD, and D2

This paper reports a theoretical study of the dependence of the E 1Sigma(+)g v(E) = 0, J-X 1Sigma(+)g, v(X),J transitions in H2, HD, and D2 on the initial vibrational and rotational quantum numbers v(X) and J. The results demonstrate the concerted nature of two-photon transitions. The magnitude of the two-photon transition moment increases with v(X) between 0 and 2, then decreases rapidly at higher v(X). The J dependence of the two-photon transition moment is most strongly affected by the changes in vibrational wave functions caused by centrifugal distortion of the vibrational potential. It is shown that the J variation can be used as a probe of resonant tunneling in the double-well potential of the E,F state.

Huo, Winifred M.↗

NASA NTRS1991

Quantitative determination of H2, HD, and D2 internal-state distributions by (2+1) resonance-enhanced multiphoton ionization

Results are presented of an experimental study of (2+1) resonance-enhanced multiphoton ionization (REMPI) detection of H2, HD, and D2 via the E,F two-photon transition, in which the relationship between ion signals and quantum-state populations was determined by calibration against a thermal effusive source. Vibrational and rotational correction factors were obtained for 102 rovibrational levels for v-double-prime = 0, 1, and 2 and for J-double-prime ranging from 0 to 17. These correction factors make it possible to convert ion signals into relative quantum-state populations without relying on a theoretical description of the (2+1) REMPI process.

Rinnen, Klaus-Dieter↗

NASA NTRS1990

Simple model for lambda-doublet propensities in bimolecular reactions

A simple geometric model is presented to account for lambda-doublet propensities in bimolecular reactions A + BC - AB + C. It applies to reactions in which AB is formed in a pi state, and in which the unpaired molecular orbital responsible for lambda-doubling arises from breaking the B-C bond. The lambda-doublet population ratio is predicted to be 2:1 provided that: (1) the motion of A in the transition state determines the plane of rotation of AB; (2) the unpaired pi orbital lying initially along the B-C bond may be resolved into a projection onto the AB plane of rotation and a projection perpendicular to this plane; (3) there is no preferred geometry for dissociation of ABC. The 2:1 lambda-doublet ratio is the 'unconstrained dynamics prior' lambda-doublet distribution for such reactions.

Bronikowski, Michael J.↗

NASA NTRS1989

Spatially resolved organic analysis of the Allende meteorite

The distribution of polycyclic aromatic hydrocarbons (PAHs) in the Allende meteorite has been probed with two-step laser desorption/laser multiphoton ionization mass spectrometry. This method allows direct in situ analysis with a spatial resolution of 1 sq mm or better of selected organic molecules. Spectra from freshly fractured interior surfaces of the meteorite show that PAH concentrations are locally high compared to the average concentrations found by wet chemical analysis of pulverized samples. The data suggest that the PAHs are primarily associated with the fine-grained matrix, where the organic polymer occurs. In addition, highly substituted PAH skeletons were observed. Interiors of individual chondrules were devoid of PAHs at the detection limit (about 0.05 ppm).

Zenobi, Renato↗

NASA NTRS1989

Reaction dynamics of H + O2 at 1.6 eV collision energy

The hot hydrogen atom reaction, H + O2 yields OH + O, has been studied at a center of mass collision energy of 1.6 eV. H atoms were generated by 266 nm photolysis of HI in a mixture of HI and O2 at 293 K. The OH product was probed by laser induced fluorescence and the nascent OH vibrational, rotational, and fine structure distributions were determined. The OH(v=0)/OH(v=1) vibrational branching ratio was measured to be 1.72 + or - 0.09. The data suggest that the H + O2 reaction at this collision energy proceeds via two competing mechanisms: reaction involving a long-lived complex and direct reaction.

Bronikowski, Michael J.↗