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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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NASA NTRS1985

A model for the origin of photosynthesis--III. The ultraviolet photochemistry of uroporphyrinogen

The photochemical ramifications of the high ultraviolet flux on the primordial earth prior to the formation of the ozone layer have been considered in a study of the ultraviolet photochemistry of uroporphyrinogen (urohexahydroporphyrin), a colorless compound which absorbs strongly at wavelengths less than 220 nanometers. Urohexahydroporphyrin was investigated since it is the first macrocycle formed on the biosynthetic pathway of chlorophyll and can be used to test the hypothesis that the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis. When urohexahydroporphyrin is illuminated in aqueous anaerobic solution, hydrogen gas is produced. More hydrogen gas is produced in the presence of a colloidal platinum catalyst. The products of the photooxidation of urohexahydroporphyrin are urotetrahydroporphyrin (uroporphomethene) and uroporphyrin. This research shows how the oxidation of uroporphyrinogen to uroporphyrin, the first biogenetic porphyrin, could have occurred anaerobically and abiotically on the primordial earth.

Evolution, Chemical↗

NASA NTRS1988

Additives for high-temperature liquid lubricants

A preliminary research program was conducted to demonstrate a new concept for additives to liquid lubricants. It was demonstrated that suspensions of o-phthalonitrile and a substituted 1,2-maleonitrile in mineral oil and dilute solutions of o-phthalonitrile and tetrafluoro-o-phthalonitrile extended the lifetime of bearings under boundary lubricating conditions. The solutions exhibited coefficients of friction under high loads of 0.02-0.03. These results were consistent with the hypothesis that these compounds react with the hot metal surface to form a planar lubricating film by means of a metal or metal oxide template reaction. Also, the adherence was very strong due to the chelating action of the planar macrocycles postulated to form under the experimental conditions.

Lawton, Emil A.↗

NASA NTRS1995

Aggregation-Enhanced Raman Scattering by a Water-Soluble Porphyrin

Much interest in our laboratory has focused on aggregation of organic compounds, particularly cyanine dyes and porphyrins. For this discussion we have applied absorption and Raman scattering spectroscopies to characterize aggregated TSPP (tetrakis-(p-sulfonatophynyl) porphyrin) in aqueous solution. Based on concentration, pH and ionic strength dependence of TSPP absorption, we deduce that aggregation evolves through the formation of TSPP diacid and that the diacid is the repeating unit in the aggregate. The Raman bands of TSPP in strongly acidic solution lead us further to conclude that vibrations of adjacent molecules are perturbed in a fashion that is consistent with the pyrrolic ring in the porphinato macrocycle being ruffled, and that two aggregate arrangements occur: specifically J- and H-type aggregates. Furthermore, aggregation enhancement is advanced as a viable mechanism to explain enhanced Raman Scattering for homogeneous aqueous phase TSPP, where the surface-enhancement mechanism is not applicable.

Akins, Daniel L.↗