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NASA NTRS2009

Combustion of Organic Molecules by the Thermal Decomposition of Perchlorate Salts: Implications for Organics at the Mars Phoenix Scout Landing Site

The Mars 2007 Phoenix Scout Mission successfully landed on May 25, 2008 and operated on the northern plains of Mars for 150 sols. The primary mission objective was to study the history of water and evaluate the potential for past and present habitability in Martian arctic ice-rich soil [1]. Phoenix landed near 68 N latitude on polygonal terrain created by ice layers that are a few centimeters under loose soil materials. The Phoenix Mission is assessing the potential for habitability by searching for organic molecules in the ice or icy soils at the landing site. Organic molecules are necessary building blocks for life, although their presence in the ice or soil does not indicate life itself. Phoenix searched for organic molecules by heating soil/ice samples in the Thermal and Evolved-Gas Analyzer (TEGA, [2]). TEGA consists of 8 differential scanning calorimeter (DSC) ovens integrated with a magnetic-sector mass spectrometer with a mass range of 2-140 daltons [2]. Endothermic and exothermic reactions are recorded by the TEGA DSC as samples are heated from ambient to ~1000 C. Evolved gases, including any organic molecules and their fragments, are simultaneously measured by the mass spectrometer during heating. Phoenix TEGA data are still under analysis; however, no organic fragments have been identified to date in the evolved gas analysis (EGA). The MECA Wet Chemistry Lab (WCL) discovered a perchlorate salt in the Phoenix soils and a mass 32 peak evolved between 325 and 625 C for one surface sample dubbed Baby Bear [3]. The mass 32 peak is attributed to evolved O2 generated during the thermal decomposition of the perchlorate salt. Perchlorates are very strong oxidizers when heated, so it is possible that organic fragments evolved in the temperature range of 300-600 C were combusted by the O2 released during the thermal decomposition of the perchlorate salt. The byproduct of the combustion of organic molecules is CO2. There is a prominent release of CO2 between 200-600 C for several of the Phoenix soils analyzed by TEGA. This low temperature release of CO2 might be any combination of 1) desorption of adsorbed CO2, 2) thermal decomposition of Fe- and Mg-carbonates, and 3) combustion of organic molecules [2].

Ming, D.W.↗
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 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↗
NASA NTRS2021

Identifying Molecules as Biosignatures with Assembly Theory and Mass Spectrometry

The search for evidence of life elsewhere in the universe is hard because it is not obvious what signatures are unique to life. Here we postulate that complex molecules found in high abundance are universal biosignatures as they cannot form by chance. To explore this, we developed the first intrinsic measure of molecular complexity that can be experimentally determined, and this is based upon a new approach called assembly theory which gives the molecular assembly number (MA) of a given molecule. MA allows us to compare the intrinsic complexity of molecules using the minimum number of steps required to construct the molecular graph starting from basic objects, and a probabilistic model shows how the probability of any given molecule forming randomly drops dramatically as its MA increases. To map chemical space, we calculated the MA of ca. 2.5 million compounds, and collected data which showed the complexity of a molecule can be experimentally determined by using three independent techniques including infra-red spectroscopy, nuclear magnetic resonance, and by fragmentation in a mass spectrometer, and this data has an excellent corelation with the values predicted from our assembly theory. We then set out to see if this approach could allow us to identify molecular biosignatures with a set of diverse samples from around the world, outer space, and the laboratory including prebiotic soups. The results show that there is a non-living to living threshold in MA complexity and the higher the MA for a given molecule, the more likely that it had to be produced by a biological process. This work demonstrates it is possible to use this approach to build a life detection instrument that could be deployed on missions to extra-terrestrial locations to detect biosignatures, map the extent of life on Earth, and be used as a molecular complexity scale to quantify the constraints needed to direct prebiotically plausible processes in the laboratory. Such an approach is vital if we are going to find new life elsewhere in the universe or create de-novo life in the lab.

Stuart M Marshall↗
NASA NTRS2007

The Chemistry of Multiply Deuterated Molecules in Protoplanetary Disks: I. The Outer Disk

We present new models of the deuterium chemistry in protoplanetary disks, including, for the first time, multiply deuterated species. We use these models to explore whether observations in combination with models can give us clues as to which desorption processes occur in disks.We find, in common with other authors, that photodesorption can allow strongly bound molecules such as HDO to exist in the gas phase in a layer above the midplane. Models including this process give the best agreement with the observations. In the midplane, cosmic-ray heating can desorb weakly bound molecules such as CO and N2. We find the observations suggest that N2 is gaseous in this region, but that CO must be retained on the grains to account for the observed DCO+/HCO+. This could be achieved by CO having a higher binding energy than N2 (as may be the case when these molecules are accreted onto water ice) or by a smaller cosmic-ray desorption rate for CO than assumed here, as suggested by recent theoretical work. For gaseous molecules the calculated deuteration can be greatly changed by chemical processing in the disk from the input molecular cloud values. On the grains singly deuterated species tend to retain the D/H ratio set in the molecular cloud, whereas multiply deuterated species are more affected by the disk chemistry. Consequently, the D/H ratios observed in comets may be partly set in the parent cloud and partly in the disk, depending on the molecule.

circumstellar matter↗
NASA NTRS1973

Molecule formation by inverse predissociation

The general theory of inverse predissociation is described, and is applied to specific molecules. The list of molecules which can be formed by radiative association will be lengthened considerably by considering this phenomenon. Typical rate constants for diatoms will lie in the range 10 to the minus 16th power to 10 to the minus 20th power cu cm/sec/molecule, with the heavy atom molecules such as CN, CO, or NO generally having larger rates than the hydrides. An attempt is made to point out what molecular characteristics determine the radiative association rate and also to make estimates of what rates may be expected for various interstellar molecules. The formal theory is developed, and the molecular properties are discussed which determine the inverse predissociation rate. The details of the theory as applied to specific interstellar molecules are studied.

Julienne, P. S.↗
NASA NTRS1978

The formation of molecules in interstellar clouds from singly and multiply ionized atoms

The suggestion is considered that multiply ionized atoms produced by K- and L-shell X-ray ionization and cosmic-ray ionization can undergo ion-molecule reactions and also initiate molecule production. The role of X-rays in molecule production in general is discussed, and the contribution to molecule production of the C(+) radiative association with hydrogen is examined. Such gas-phase reactions of singly and multiply ionized atoms are used to calculate molecular abundances of carbon-, nitrogen-, and oxygen-bearing species. The column densities of the molecules are evaluated on the basis of a modified version of previously developed isobaric cloud models. It is found that reactions of multiply ionized carbon with H2 can contribute a significant fraction of the observed CH in diffuse interstellar clouds in the presence of diffuse X-ray structures or discrete X-ray sources and that substantial amounts of CH(+) can be produced under certain conditions.

Langer, W. D.↗
NASA NTRS1983

Theoretical studies of photodissociation of small molecules of astrophysical importance

The radicals and ions observed in comets result from photodissociation and photoionization of molecules. According to current models, a comet is composed chiefly of a large, solid nucelus of frozen gases (parent molecules) such as H2O, HCN, and NH3. It is believed comets were formed at the same time and in the same region of space as the major planets and that their chemical composition is the same as that of the early solar system. As the comet nears the Sun, the surface heats up, liberating the frozen gases as well as dust particles. Solar radiation photodissociates the parent molecules into fragments that are observed by resonance fluorescence. Both polyatomic molecules, present in the interstellar medium, and cometary radicals were observed. Using laboratory photo-dissociation data and computer models, astronomers are attempting to identify the parent molecules that account for all observed radicals and ions.

Saxon, R. P.↗
NASA NTRS1985

Radiative relaxation of molecular vibration of the nitric oxide molecule as a possible source of the infrared Shuttle glow

A model calculation to predict infrared Shuttle flow due to the radiative relaxation of vibration of the NO molecule is presented. Space Shuttles hit atmospheric NO molecules at a very high speed and excite vibrational and rotational motions up to the temperature of 54,000 K. With the electric dipole radiation of delta v = 1, 2, 3, and particularly 4 (v is the vibrational quantum number), the excited NO molecules emit infrared radiation before they collide with other molecules. The total radiation power is estimated to be 170 A micro-W, where A is the cross-section area of the Shuttle in sq m if no adsorption of the NO molecule takes place on the Shuttle surface. The intensity of each infrared line is calculated as a function of time, including all vibrational states up to v = 35.

Mizushima, M.↗
NASA NTRS1989

Diffusion and infrared properties of molecules in ice mantles

Within dense molecular clouds the formation of frozen icy mantles on interstellar dust grains is thought to be the result of various growth conditions. The molecules, which make up the ice mantles are probably completely mixed. To study the physical properties of such ice mixtures the experiments were performed on the evaporation processes and on the spectroscopic properties of CO, CO2, and CH4 in water rich ices. The decrease in concentration of volatile molecules in ice samples deposited at 10 K and subsequently heated is found to occur essentially in two steps. The first one, corresponding to an evaporation of part of the volatile molecules, starts at about 25 K for CO, 32 K for CH4, and 70 K for CO2. During the crystallization of H2O ice at temperatures greater than 120 K a second evaporation occurs leading to the complete disappearance of the volatile molecules in the solid phase. The main astrophysical implications of the diffusion and spectroscopic behaviors are presented. The possible effects of a heating source on the fraction of volatile molecules, such as CO trapped in grain mantles, are discussed.

Schmitt, Bernard↗
NASA NTRS1992

Dissociation energy of molecules in dense gases

A general approach is presented for calculating the reduction of the dissociation energy of diatomic molecules immersed in a dense (n = less than 10 exp 22/cu cm) gas of molecules and atoms. The dissociation energy of a molecule in a dense gas differs from that of the molecule in vacuum because the intermolecular forces change the intramolecular dynamics of the molecule, and, consequently, the energy of the molecular bond.

Kunc, J. A.↗
NASA NTRS1995

Computing Fluxes Of Molecules On And Near A Spacecraft

Molecular Flux (MOLFLUX) computer code versatile program used to compute following environmental effects induced by spacecraft: fluxes of molecules to, and deposition of molecules on, surfaces; densities and column densities of molecules in surrounding space, and return fluxes of molecules to surfaces caused by both collisions of molecules with ambient atmosphere and by self-scattering. Includes capability to predict buildup in density of ambient gas in front of surfaces exposed to ram conditions by specifying ambient flux rates for all species impinging on surfaces. Surface chemical reactions represented as rates of emission from surfaces. User has option to modify spacecraft configurations and sources of contamination, and to choose which critical surfaces to examine. Written in FORTRAN and C language.

Ehlers, H. K.↗
NASA NTRS1996

Computing Fluxes Of Molecules On And Near A Spacecraft

Molecular Flux (MOLFLUX) computer code is versatile program used to compute following conditions on and near spacecraft: fluxes of molecules to, and deposition of molecules on, surfaces; densities and column densities of molecules in surrounding space, and return fluxes of molecules to surfaces caused by both collisions of molecules with ambient atmosphere and by self-scattering. User has option to modify spacecraft configurations and sources of contamination and to choose which critical surfaces to examine. Written in FORTRAN and C language. Three machine versions available: VAX version (MSC-22260), HP version (MSC-22565), and Cray version (MSC-22566).

Ehlers, H. K.↗
NASA NTRS1959

Heat Transfer from Cylinders in Transition From Slip Flow to Free-Molecule Flow

Over 600 measured heat-transfer coefficients in the transition from slip to free-molecule flow have been correlated by using the Nusselt number Nu as a function of the Knudsen Kn and Reynolds Re (or Mach M) numbers. The experimental range for these heat-transfer data from transverse cylinders in air corresponds to the following dimensionless groups: M, 0.10 to 0.90; Re, 0.03 to 11.5; Kn, 0.10 to 5.0. The total air temperature T(sub t) was maintained constant at 80 F, but wire temperature was Varied from 150 to 580 F. At Kn=0.10, Nu extrapolates smoothly into slip-flow empirical curves that show Nu as a function of Re and M or Kn. The correlation gradually changes from the square root of Re(sub t) dependence characteristic of continuum flow to first-power Re dependence as Kn increases (decreasing Re). At the experimental limit Kn ft 5.0, the Nu data correlate with a mean fractional error of 413 percent by the prediction of free-molecule-flow theory. In comparing experimental results with theory, an accommodation coefficient of 0.57+/-0.07 was inferred from the heat-transfer data, which were obtained with etched tungsten wire in air. The wire recovery temperature T(sub e) was measured and compared with existing data and theory in terms of a ratio eta(equivalent to T(sub e)/T(sub t). The results can be divided into three groups by Kn criteria: For Kn less than 2.01, eta is independent of Kn, and eta decreases from 1.0 to 0.97 as M increases from 0 to 0.90; for 2.0 less than Kn less than 5.0, eta is a function of both Kn and M in this transition region to fully developed free-molecule flow; and for Kn greater than 5.0, eta predicted by free-molecule-flow theory is observed and increases from 1.0 to 1.08 as M increases from 0 to 0.90, again independent of Kn. Therefore, these T(sub e) data provide a guide to the boundary of fully developed free-molecule flow, which is.inferred from this research to exist for Kn greater than 5.0. This boundary criterion is substantiated by other published data on T(sub e) at supersonic speeds.

Cybulski, Ronald J.↗
NASA NTRS2001

Carbon Nanotube Biosensors for Space Molecule Detection and Clinical Molecular Diagnostics

Both space molecule detection and clinical molecule diagnostics need to develop ultra sensitive biosensors for detection of less than attomole molecules such as amino acids for DNA. However all the electrode sensor systems including those fabricated from the existing carbon nanotubes, have a background level of nA (nanoAmp). This has limited DNA or other molecule detection to nA level or molecules whose concentration is, much higher than attomole level. A program has been created by NASA and NCI (National Cancer Institute) to exploit the possibility of carbon nanotube based biosensors to solve this problem for both's interest. In this talk, I will present our effort on the evaluation and novel design of carbon nanotubes as electrode biosensors with strategies to minimize background currents while maximizing signal intensity.The fabrication of nanotube electrode arrays, immobilization of molecular probes on nanotube electrodes and in vitro biosensor testing will also be discussed.

Han, Jie↗
NASA NTRS1999

Molecules from Space and the Origin of Life

There is a growing concensus among space scientists that frozen molecules from space helped to make the Earth the pleasant place that it is today, and helped Life start on Earth, and perhaps elsewhere. The chain of logic that led scientists to posit a connection between extraterrestrial molecules and the origin of life is as follows. 1) The rapidity with which life arose demands that conditions on Earth were conducive to the formation of life very early on. 2) There is reason to believe that comets and meteorites fell oil the Earth from its inception. 3) We now know that comets and meteorites are replete with complex organic compounds, some of which resemble those in living systems. 4) Perhaps the input of molecules from comets and meteorites provided crucial constituents to the primordial soup and Jump started life on Earth. 5) These molecules formed out in deep space long before the Earth ever existed, by processes that we can reproduce in the laboratory. 6) The fact that organic molecules are seen by astronomers throughout our galaxy and in others makes it seem likely that they were (and are) available to help start life in other planetary systems.

Bernstein Max P.↗
NASA NTRS1997

Energetics of the lattice: packing elements in crystals of four-stranded intercalated cytosine-rich DNA molecules

Condensation of single molecules from solution into crystals represents a transition between distinct energetic states. In solution, the atomic interactions within the molecule dominate. In the crystalline state, however, a set of additional interactions are formed between molecules in close contact in the lattice--these are the packing interactions. The crystal structures of d(CCCT), d(TAACCC), d(CCCAAT), and d(AACCCC) have in common a four-stranded intercalated cytosine segment, built by stacked layers of cytosine.cytosine+ (C.C+) base pairs coming from two parallel duplexes that intercalate into each other with opposite polarity. The intercalated cytosine segments in these structures are similar in their geometry, even though the sequences crystallized in different space groups. In the crystals, adenine and thymine residues of the sequences are used to build the three-dimensional crystal lattice by elaborately interacting with symmetry-related molecules. The packing elements observed provide novel insight about the copious ways in which nucleic acid molecules can interact with each other--for example, when folded in more complicated higher order structures, such as mRNA and chromatin.

Non-NASA Center↗
NASA NTRS2004

Meteors do not break exogenous organic molecules into high yields of diatomics

Meteoroids that dominate the Earth's extraterrestrial mass influx (50-300 microm size range) may have contributed a unique blend of exogenous organic molecules at the time of the origin of life. Such meteoroids are so large that most of their mass is ablated in the Earth's atmosphere. In the process, organic molecules are decomposed and chemically altered to molecules differently from those delivered to the Earth's surface by smaller (<50 microm) micrometeorites and larger (>10 cm) meteorites. The question addressed here is whether the organic matter in these meteoroids is fully decomposed into atoms or diatomic compounds during ablation. If not, then the ablation products made available for prebiotic organic chemistry, and perhaps early biology, might have retained some memory of their astrophysical nature. To test this hypothesis we searched for CN emission in meteor spectra in an airborne experiment during the 2001 Leonid meteor storm. We found that the meteor's light-emitting air plasma, which included products of meteor ablation, contained less than 1 CN molecule for every 30 meteoric iron atoms. This contrasts sharply with the nitrogen/iron ratio of 1:1.2 in the solid matter of comet 1P/Halley. Unless the nitrogen content or the abundance of complex organic matter in the Leonid parent body, comet 55P/Tempel-Tuttle, differs from that in comet 1P/Halley, it appears that very little of that organic nitrogen decomposes into CN molecules during meteor ablation in the rarefied flow conditions that characterize the atmospheric entry of meteoroids approximately 50 microm-10 cm in size. We propose that the organics of such meteoroids survive instead as larger compounds.

Meteoroids↗