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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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25 records · Page 2

Photochemistry of porphyrins: a model for the origin of photosynthesis

A series of porphyrins and catalysts has been prepared as a model for the origin of photosynthesis on the primordial earth. These compounds have been used to test the hypotheses that (1) the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis, and (2) the proto-photosythetic function of biogenetic porphyrins (biosynthetic chlorophyll precursors) was the oxidation of organic molecules by photoexcited porphyrins with the attendant emission of molecular hydrogen. This paper describes experiments in which photoexcited biogenetic porphyrins oxidize ethylenediamine tetraacetic acid (EDTA). The concomitant reduction of protons to hydrogen gas occurs in the presence of a colloidal platinum catalyst. The addition of methyl viologen, a one-electron shuttle, increases the amount of molecular hydrogen generated during long irradiations and the quantum yield of hydrogen production. When the porphyrin and catalyst are held in association by molecular complexes, the increased efficiency of electron transfer produces higher yields of hydrogen gas.

Hydrogen/chemistry↗

UV irradiation of polycyclic aromatic hydrocarbons in ices: production of alcohols, quinones, and ethers

Polycyclic aromatic hydrocarbons (PAHs) in water ice were exposed to ultraviolet (UV) radiation under astrophysical conditions, and the products were analyzed by infrared spectroscopy and mass spectrometry. Peripheral carbon atoms were oxidized, producing aromatic alcohols, ketones, and ethers, and reduced, producing partially hydrogenated aromatic hydrocarbons, molecules that account for the interstellar 3.4-micrometer emission feature. These classes of compounds are all present in carbonaceous meteorites. Hydrogen and deuterium atoms exchange readily between the PAHs and the ice, which may explain the deuterium enrichments found in certain meteoritic molecules. This work has important implications for extraterrestrial organics in biogenesis.

NASA Center ARC↗

Structure and dynamics of amorphous water ice

Further insight into the structure and dynamics of amorphous water ice, at low temperatures, was obtained by trapping in it Ar, Ne, H2, and D2. Ballistic water-vapor deposition results in the growth of smooth, approximately 1 x 0.2 micrometer2, ice needles. The amorphous ice seems to exist in at least two separate forms, at T < 85 K and at 85 < T < 136.8 K, and transform irreversibly from one form to the other through a series of temperature-dependent metastable states. The channels formed by the water hexagons in the ice are wide enough to allow the free penetration of H2 and D2 into the ice matrix even in the relatively compact cubic ice, resulting in H2-(D2-) to-ice ratios (by number) as high as 0.63. The larger Ar atoms can penetrate only into the wider channels of amorphous ice, and Ne is an intermediate case. Dynamic percolation behavior explains the emergence of Ar and Ne (but not H2 and D2) for the ice, upon warming, in small and big gas jets. The big jets, each containing approximately 5 x 10(10) atoms, break and propel the ice needles. Dynamic percolation also explains the collapse of the ice matrix under bombardment by Ar , at a pressure exceeding 2.6 dyn cm-2, and the burial of huge amounts of gas inside the collapsed matrix, up to an Ar-to-ice of 3.3 (by number). The experimental results could be relevant to comets, icy satellites, and icy grain mantles in dense interstellar clouds.

NASA Program Exobiology↗

Stable light isotope biogeochemistry of hydrothermal systems

The stable isotopic composition of the elements O, H, S and C in minerals and other chemical species can indicate the existence, extent, conditions and the processes (including biological activity) of hydrothermal systems. Hydrothermal alteration of the 18O/16O and D/H values of minerals can be used to detect fossil systems and delineate their areal extent. Water-rock interactions create isotopic signatures which indicate fluid composition, temperature, water-rock ratios, etc. The 18O/16O values of silica and carbonate deposits tend to increase with declining temperature and thus help to map thermal gradients. Measurements of D/H values can help to decipher the origin(s) of hydrothermal fluids. The 34S/32S and 13C/12C values of fluids and minerals reflect the origin of the S and C as well as oxygen fugacities and key redox processes. For example, a wide range of 34S/32S values which are consistent with equilibration below 100 degrees C between sulfide and sulfate can be attributed to sulfur metabolizing bacteria. Depending on its magnitude, the difference in the 13C/12C value of CO2 and carbonates versus organic carbon might be attributed either to equilibrium at hydrothermal temperatures or, if the difference exceeds 1% (10/1000), to organic biosynthesis. Along the thermal gradients of thermal spring outflows, the 13C/12C value of carbonates and 13C-depleted microbial organic carbon increases, principally due to the outgassing of relatively 13C-depleted CO2.

Review, Tutorial↗

Kinetics of organic transformations under mild aqueous conditions: implications for the origin of life and its metabolism

The rates of thermal transformation of organic molecules containing carbon, hydrogen, and oxygen were systematically examined in order to identify the kinetic constraints that governed origin-of-life organic chemistry under mild aqueous conditions. Arrhenius plots of the kinetic data were used to estimate the reaction of half-lifes at 50 degrees C. This survey showed that hydrocarbons and organic substances containing a single oxygenated group were kinetically the most stable; whereas organic substances containing two oxygenated groups in which one group was an alpha- or beta-positioned carbonyl group were the most reactive. Compounds with an alpha- or beta-positioned carbonyl group (aldehyde or ketone) had rates of reaction that were up to 10(24)-times faster than rates of similar molecules lacking the carbonyl group. This survey of organic reactivity, together with estimates of the molecular containment properties of lipid vesicles and liquid spherules, indicates that an origins process in a small domain that used C,H,O-intermediates had to be catalytic and use the most reactive organic molecules to prevent escape of its reaction intermediates.

Biogenesis↗

Hydrogen emission in meteors as a potential marker for the exogenous delivery of organics and water

We detected hydrogen Balmer-alpha (H(alpha)) emission in the spectra of bright meteors and investigated its potential use as a tracer for exogenous delivery of organic matter. We found that it is critical to observe the meteors with high enough spatial resolution to distinguish the 656.46 nm H(alpha) emission from the 657.46 nm intercombination line of neutral calcium, which was bright in the meteor afterglow. The H(alpha) line peak stayed in constant ratio to the atmospheric emissions of nitrogen during descent of the meteoroid. If all of the hydrogen originates in the Earth's atmosphere, the hydrogen atoms are expected to have been excited at T = 4400 K. In that case, we measured an H(2)O abundance in excess of 150 +/- 20 ppm at 80-90 km altitude (assuming local thermodynamic equilibrium in the air plasma). This compares with an expected <20 ppm from H(2)O in the gas phase. Alternatively, meteoric refractory organic matter (and water bound in meteoroid minerals) could have caused the observed H(alpha) emission, but only if the line is excited in a hot T approximately 10000 K plasma component that is unique to meteoric ablation vapor emissions such as Si(+). Assuming that the Si(+) lines of the Leonid spectrum would need the same hot excitation conditions, and a typical [H]/[C] = 1 in cometary refractory organics, we calculated an abundance ratio [C]/[Si] = 3.9 +/- 1.4 for the dust of comet 55P/Tempel-Tuttle. This range agreed with the value of [C]/[Si] = 4.4 measured for comet 1P/Halley dust. Unless there is 10 times more water vapor in the upper atmosphere than expected, we conclude that a significant fraction of the hydrogen atoms in the observed meteor plasma originated in the meteoroid.

Water↗

High-resolution spectroscopy of H2SO4, HDSO4, and D2SO4 vapor in the region 1200-10,000 cm(-1)

The high-resolution (0.05 cm(-1)) spectra of gas-phase H2SO4, HDSO4, and D2SO4 were measured over the frequency region 1200-10,000 cm(-1) using Fourier-transform infrared spectroscopy. The increased resolution of this work compared with previous studies has lead to an improved vibrational analysis of H2SO4. This study has answered unresolved questions about combination bands and overlapping features from previous gas-phase spectroscopic studies of H2SO4 and marks the first experimental measurement of the nu8 and nu15 torsional vibrations in this molecule. This work leads to a brief discussion on vibrational mode mixing in sulfuric acid.

Deuterium/chemistry↗