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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

Cytochromes and iron sulfur proteins in sulfur metabolism of phototrophic bacteria

Dissimilatory sulfur metabolism in phototrophic sulfur bacteria provides the bacteria with electrons for photosynthetic electron transport chain and, with energy. Assimilatory sulfate reduction is necessary for the biosynthesis of sulfur-containing cell components. Sulfide, thiosulfate, and elemental sulfur are the sulfur compounds most commonly used by phototrophic bacteria as electron donors for anoxygenic photosynthesis. Cytochromes or other electron transfer proteins, like high-potential-iron-sulfur protein (HIPIP) function as electron acceptors or donors for most enzymatic steps during the oxidation pathways of sulfide or thiosulfate. Yet, heme- or siroheme-containing proteins themselves undergo enzymatic activities in sulfur metabolism. Sirohemes comprise a porphyrin-like prosthetic group of sulfate reductase. eenzymatic reactions involve electron transfer. Electron donors or acceptors are necessary for each reaction. Cytochromes and iron sulfur problems, are able to transfer electrons.

Fischer, U.↗
NASA NTRS1988

Electrocatalytic reduction of oxygen on modified oxide surfaces

A first step which frequently occurs in the reduction of dioxygen, e.g., at the cathode of the alkaline fuel cell, is the two-electron reduction to the peroxyl ion, HO bar 2. For the efficiency of the fuel cell, this ion must be further reduced, or decomposed, to OH(-). Rate constants for HO bar 2 decomposition have been determined in 31 percent KOH at 25 C for the following catalysts in the form of suspended powders and Teflon-bonded electrodes: Pt, Au, cobalt tetrametoxyl phenyl porphyrin (CoTMPP), and La sub 0.5Pb sub 0.5MnO3. Rates were normalized to unit surface area measured by several methods as suitable. Where possible, four methods were used to measure rate constants: gasometric, oxygen probe, rotating disk electrode, and open-circuit potential decay. Steady-state polarization was also tried but was not as satisfactory. Comparisons are given for the methods in regard to reliability, applicability to the material, and convenience.

Chaffins, Scott A.↗
NASA NTRS1989

Origins of etioporphyrins in sediments - Evidence from stable carbon isotopes

In samples of the Julia Creek and Condor oil shales (Australia, Albian, and early Tertiary, respectively) etioporphyrin III is significantly depleted in C-13 (4 per mil) relative to porphyrins derived from chlorophylls. This isotopic difference suggests a large contribution from some independent source. The haem group found in cytochromes derived from microbial sources is the most likely candidate.

Boreham, Christopher J.↗
NASA NTRS1989

An isotopic study of biogeochemical relationships between carbonates and organic carbon in the Greenhorn Formation

Carbon-isotopic compositions of total carbonate, inoceramid carbonate, micritic carbonate, secondary cements, total organic carbon, and geoporphyrins have been measured in 76 different beds within a 17-m interval of a core through the Greenhorn Formation, an interbedded limestone and calcareous shale unit of Cretaceous age from the Western Interior Seaway of North America. Results are considered in terms of variations in the processes of primary production and in secondary processes. It is shown that the porphyrin isotopic record reflects primary isotopic variations more closely than the TOC isotopic record and that, in these sediments, TOC is enriched in C-13 relative to its primary precursor by 0.6 to 2.8 percent. This enrichment is attributed to isotope effects within the consumer foodweb and is associated with respiratory heterotrophy. Variation in this secondary enrichment are correlated with variations in the isotopic composition of marine carbonate.

Hayes, J. M.↗
NASA NTRS1990

The photochemical origins of life and photoreaction of ferrous ion in the archaean oceans

A general argument is made for the photochemical origins of life. A constant flux of free energy is required to maintain the organized state of matter called life. Solar photons are the unique source of the large amounts of energy probably required to initiate this organization and certainly required for the evolution of life to occur. The completion of this argument will require the experimental determination of suitable photochemical reactions. It is shown that biogenetic porphyrins readily photooxidize substrates and emit hydrogen in the presence of a catalyst. These results are consistent with the Granick hypothesis, which relates a biosynthetic pathway to its evolutionary origin. It has been shown that photoexcitation of ferrous ion at neutral pH with near ultraviolet light produces hydrogen with high quantum yield. This same simple system may reduce carbon dioxide to formaldehyde and further products. These reactions offer a solution to the dilemma confronting the Oparin-Urey-Miller model of the chemical origin of life. If carbon dioxide is the main form of carbon on the primitive earth, the ferrous photoreaction may provide the reduced carbon necessary for the formation of amino acids and other biogenic molecules. These results suggest that this progenitor of modern photosynthesis may have contributed to the chemical origins of life.

Mauzerall, David C.↗
NASA NTRS1991

Compositional studies of primitive asteroids

The aqueous alteration history in the solar system are studied through acquiring additional CCD reflectance spectra in the blue-UV through near-IR spectral region and analyzing these spectra for information about iron oxides in phyllosilicates identified in the CM and CI carbonaceous chondrites. Emphasis is on the main-belt and Cybele primitive asteroids, as these asteroids show spectral diversity and are also spectral analogues for known meteorite samples. The porphyrin bands found in organics near 0.4 micron is also sought.

Vilas, Faith↗
NASA NTRS1993

Ferric iron in primitive asteroids - A 0.43-micron absorption feature

A search of reflectance spectra of C- P-, D- and S-class asteroids to hunt for the Soret band near 0.4 micron that is indicative of porphyrins yielded an identification of an 0.43 micron absorption feature in 11 primitive asteroids of the C, P, and G classes and in one S-class asteroid. It is proposed that the feature is an Fe(3+) spin-forbidden transition in aqueously altered material, possibly located near 0.43 micron due to an enhancement effect similar to the mechanism operating in jarosite. The significance of the feature for the aqueous alteration history of these asteroids is addressed.

Vilas, Faith↗
NASA NTRS1994

Surface acoustic wave oxygen sensor

A surface acoustic wave (SAW) device that responds to oxygen pressure was developed by coating a 158 MHz quartz surface acoustic wave (SAW) device with an oxygen binding agent. Two types of coatings were used. One type was prepared by dissolving an oxygen binding agent in a toluene solution of a copolymer containing the axial ligand. A second type was prepared with an oxygen binding porphyrin solution containing excess axial ligand without a polymer matrix. In the polymer based coatings, the copolymer served to provide the axial ligand to the oxygen binding agent and as a coating matrix on the surface of the SAW device. The oxygen sensing SAW device has been shown to bind oxygen following a Langmuir isotherm and may be used to measure the equilibrium constant of the oxygen binding compound in the coating matrix.

Collman, James P.↗
NASA NTRS1994

Mechanism of phosphorescence quenching in photomagnetic molecules determined by positron annihilation spectroscopy

Platinum Octaethyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state (T(sub 1)) is readily quenched by the oxygen (O2) molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the (T(sub 1)-S(sub 0)) transitions is still unknown. The diamagnetic S(sub n) singlet states, which feed T(sub 1) states via intersystem crossings, would presumably not be affected by O2. It must be the magnetic T(sub 1) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of (S(sub n).02) complexes which can also eventually reduce the population of the T(sub 1) states (i.e. quench phosphorescence). This is possible since higher triplet states in (Pt-OEP) are admixed with the S(sub n) states via spin orbit interactions. The experimental procedures and the results of various measurements are discussed in this paper.

Singh, Jag J.↗
NASA NTRS1994

Mechanism of phosphorescence quenching in photomagnetic molecules determined by positron annihilation spectroscopy

Platinum Octaethyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state (T(sub 1)) is readily quenched by the oxygen (O2) molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the (T(sub 1) - S(sub 0)) transitions is still unknown. The diamagnetic S(sub n) singlet states, which feed T(sub 1) states via intersystem crossings, would presumably not be affected by O2. It must be the magnetic T(sub 1) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of (S(sub n) central dot O2) complexes which can also eventually reduce the population of the T(sub 1) states (i.e. quench phosphorescence). This is possible since higher triplet states in (Pt.OEP) are admixed with the S(sub n) states via spin orbit interactions. The experimental procedures and the results of various measurements are discussed in this paper.

Singh, Jag J.↗
NASA NTRS1996

Investigation of Oxygen-Induced Quenching of Phosphorescence in Photoexcited Aromatic Molecules by Positron Annihilation Spectroscopy

Platinum OctaEthyl Porphyrin (Pt.OEP) is an efficient phosphor under ultraviolet excitation. The phosphorescent triplet state P(T(Sup 1)) is readily quenched by the oxygen O2 molecules. This phenomenon is being utilized as the basis for global air pressure measurements in aerodynamic facilities at various laboratories. The exact mechanism by which O2 molecules quench the P(T(Sup 1) approaches P(S(Sub O)) transitions is still unknown. The diamagnetic singlet states P(S(Sub n)), which feed P(T(Sub 1)) states via intersystem crossings, would presumably not be affected by O2. It must be only the magnetic P(T(Sub 1)) states, which can interact with the paramagnetic O2 molecules, that are affected. However, our positron lifetime and Doppler broadening studies suggest the formation of O2P(S(Sub n)), complexes which can also eventually reduce the population of the P(T(Sub 1)) states (i.e., quench phosphorescence). This reduction is possible because higher triplet states in (Pt.OEP) are admixed with the P(S(Sub 1)), states via spin orbit interactions. The experimental procedures and the results of various measurements are presented in this paper.

Singh, Jag J.↗
NASA NTRS1995

Laboratory Studies of DIB Carriers

Spectroscopic studies of the following potential diffuse interstellar band (DIB) carriers are reviewed: unspecified organics, carbon chains, polycyclic aromatic hydrocarbons (PAHs), fullerenes and derivatives, as well as porphyrins and related material. An assessment of each is given, along with suggestions for further experimental studies needed to fully test each candidate. Of the experimental techniques in common use matrix isolation spectroscopy with neon matrices is the most appropriate for the DIBs. The low vapor pressure and high reactivity of these materials preclude gas phase studies on many of these species. At this point, given the type and quality of published data available, carbon chains and PARs are the most promising candidates for a number of the DIBs.

Allamandola, L. J.↗
NASA NTRS1997

Neocytolysis Contributes to the Anemia of Renal Disease

Neocytolysis is a recently described physiologic process effecting selective hemolysis of young red blood cells in circumstances of plethora. Erythropoietin depression appears to initiate the process, providing rationale to investigate its contributions to the anemia of renal disease. When erythropoietin therapy was withheld, four of five stable hemodialysis patients demonstrated Cr-51 red cell survival patterns indicative of neocytolysis; red cell survival was short in the first 9 days, then normalized. Two of these patients received oral (13)C-glycine and (15)N-glycine and showed pathologic enrichment of stool porphyrins by the most recently ingested isotope when EPO therapy was held. This confirms selective hemolysis of newly-released red cells. (One patient had chronic hemolysis by isotope studies of blood and stool.) Thus, neocytolysis can contribute to the anemia of renal disease and explains some unresolved issues about such anemia. One implication is the prediction that intravenous bolus erythropoietin therapy is metabolically and economically inefficient compared to lower doses given more frequently subcutaneously.

Rice, Lawrence↗
NASA NTRS1976

Lead Poison Detection

With NASA contracts, Whittaker Corporations Space Science division has developed an electro-optical instrument to mass screen for lead poisoning. Device is portable and detects protoporphyrin in whole blood. Free corpuscular porphyrins occur as an early effect of lead ingestion. Also detects lead in urine used to confirm blood tests. Test is inexpensive and can be applied by relatively unskilled personnel. Similar Whittaker fluorometry device called "drug screen" can measure morphine and quinine in urine much faster and cheaper than other methods.

Source record↗
NASA NTRS1997

Redox chemistry at liquid/liquid interfaces

The interface between two immiscible liquids with immobilized photosynthetic pigments can serve as the simplest model of a biological membrane convenient for the investigation of photoprocesses accompanied by spatial separation of charges. As it follows from thermodynamics, if the resolvation energies of substrates and products are very different, the interface between two immiscible liquids may act as a catalyst. Theoretical aspects of charge transfer reactions at oil/water interfaces are discussed. Conditions under which the free energy of activation of the interfacial reaction of electron transfer decreases are established. The activation energy of electron transfer depends on the charges of the reactants and dielectric permittivity of the non-aqueous phase. This can be useful when choosing a pair of immiscible solvents to decrease the activation energy of the reaction in question or to inhibit an undesired process. Experimental interfacial catalytic systems are discussed. Amphiphilic molecules such as chlorophyll or porphyrins were studied as catalysts of electron transfer reactions at the oil/water interface.

Non-NASA Center↗
NASA NTRS1990

Origin of petroporphyrins. 2. Evidence from stable carbon isotopes

Compared with the carbon-13 isotopic composition of the ubiquitous C32DPEP (DPEP, deoxophylloerythroetioporphyrin) the heavy but equivalent carbon-13 isotopic composition for the porphyrin structures 15(2)-methyl-15,17-ethano-17-nor-H-C30DPEP and 15,17-butano-, 13,15-ethano-13(2),17-propano-, and 13(1)-methyl-13,15-ethano-13(2),17-propanoporphyrin suggests a common precursor, presumably chlorophyll c, for these petroporphyrins isolated from the marine Julia Creek oil shale and the lacustrine Condor oil shale. Similarly, the heavy but variable carbon-13 isotopic composition of 7-nor-H-C31DPEP compared with C32DPEP is consistent with an origin from both chlorophyll b and chlorophyll c3. The equivalent carbon-13 isotopic composition for 13(2)-methyl-C33DPEP compared with C32DPEP suggests a common origin resulting from a weighted average of chlorophyll inputs.

NASA Program Exobiology↗
NASA NTRS1992

Fractionation of carbon isotopes by phytoplankton and estimates of ancient CO2 levels

Reports of the 13C content of marine particulate organic carbon are compiled and on the basis of GEOSECS data and temperatures, concentrations, and isotopic compositions of dissolved CO2 in the waters in which the related phytoplankton grew are estimated. In this way, the fractionation of carbon isotopes during photosynthetic fixation of CO2 is found to be significantly correlated with concentrations of dissolved CO2. Because ancient carbon isotopic fractionations have been determined from analyses of sedimentary porphyrins [Popp et al., 1989], the relationship between isotopic fractionation and concentrations of dissolved CO2 developed here can be employed to estimate concentrations of CO2 dissolved in ancient oceans and, in turn, partial pressures of CO2 in ancient atmospheres. The calculations take into account the temperature dependence of chemical and isotopic equilibria in the dissolved-inorganic-carbon system and of air-sea equilibria. Paleoenvironmental temperatures for each sample are estimated from reconstructions of paleogeography, latitudinal temperature gradients, and secular changes in low-latitude sea surface temperature. It is estimated that atmospheric partial pressures of CO2 were over 1000 micro atm 160 - 100 Ma ago, then declined to values near 300 micro atm during the next 100 Ma. Analysis of a high-resolution record of carbon isotopic fractionation at the Cenomanian-Turonian boundary suggests that the partial pressure of CO2 in the atmosphere was drawn down from values near 840 micro atm to values near 700 micro atm during the anoxic event.

NASA Discipline Exobiology↗
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↗