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At least 235 records · Page 13

Determining divergence times with a protein clock: update and reevaluation

A recent study of the divergence times of the major groups of organisms as gauged by amino acid sequence comparison has been expanded and the data have been reanalyzed with a distance measure that corrects for both constraints on amino acid interchange and variation in substitution rate at different sites. Beyond that, the availability of complete genome sequences for several eubacteria and an archaebacterium has had a great impact on the interpretation of certain aspects of the data. Thus, the majority of the archaebacterial sequences are not consistent with currently accepted views of the Tree of Life which cluster the archaebacteria with eukaryotes. Instead, they are either outliers or mixed in with eubacterial orthologs. The simplest resolution of the problem is to postulate that many of these sequences were carried into eukaryotes by early eubacterial endosymbionts about 2 billion years ago, only very shortly after or even coincident with the divergence of eukaryotes and archaebacteria. The strong resemblances of these same enzymes among the major eubacterial groups suggest that the cyanobacteria and Gram-positive and Gram-negative eubacteria also diverged at about this same time, whereas the much greater differences between archaebacterial and eubacterial sequences indicate these two groups may have diverged between 3 and 4 billion years ago.

NASA Discipline Exobiology↗

An analysis of the metabolic theory of the origin of the genetic code

A computer program was used to test Wong's coevolution theory of the genetic code. The codon correlations between the codons of biosynthetically related amino acids in the universal genetic code and in randomly generated genetic codes were compared. It was determined that many codon correlations are also present within random genetic codes and that among the random codes there are always several which have many more correlations than that found in the universal code. Although the number of correlations depends on the choice of biosynthetically related amino acids, the probability of choosing a random genetic code with the same or greater number of codon correlations as the universal genetic code was found to vary from 0.1% to 34% (with respect to a fairly complete listing of related amino acids). Thus, Wong's theory that the genetic code arose by coevolution with the biosynthetic pathways of amino acids, based on codon correlations between biosynthetically related amino acids, is statistical in nature.

NASA Discipline Exobiology↗

Protein structure, electron transfer and evolution of prokaryotic photosynthetic reaction centers

Photosynthetic reaction centers from a variety of organisms have been isolated and characterized. The groups of prokaryotic photosynthetic organisms include the purple bacteria, the filamentous green bacteria, the green sulfur bacteria and the heliobacteria as anoxygenic representatives as well as the cyanobacteria and prochlorophytes as oxygenic representatives. This review focuses on structural and functional comparisons of the various groups of photosynthetic reaction centers and considers possible evolutionary scenarios to explain the diversity of existing photosynthetic organisms.

NASA Discipline Exobiology↗

Ice Chemistry Through Quiescent Dust In IC5146

IC 5146 is a nearby (200pc) dark cloud complex in Cygnus. The lack of star formation activity makes it an excellent laboratory for the study of the chemical complexity in the earliest stages of dense molecular cloud evolution. We have used the Spitzer Infrared Spectrometer (IRS) to probe dust along 10 sight-lines toward K-Giant background stars, sampling a range of visual extinction from 2-20mag. Here we present 5-20micron spectra and correlation studies of the 6.0micron water-ice band and 9.7micron silicate absorption band with Av for a sample of our Spitzer program sources. Our IC5146 Spitzer data indicate grain growth and ice formation occurs early in the history of dense cloud formation. Each sight-line observed reveals the 9.7micron amorphous silicate absorption band. The highest Av sightlines show clear detections of ices at 6.0micron (water-ice mixture), 6.85micron (processed ice) and 15.2micron (CO2). However, sight-lines in the low-to-mid Av range provide intriguing variations. We may have the first example of two objects, one with ice features and one without, seen through the same cloud sightline with similar Av approx. 6 and similar silicate band optical depths. Also, the nominally expected linear correlation of Av with silicate band depth does not appear to hold for this cloud (turnover at Av approx.10-12). Both trends imply complexities in the grain growth at one of the earliest stages of dust and ice interaction ever observed. The highest extinction source in our sample, Av=20, reveals the 6.0micron (water), 6.85micron (processed ice), 9.7micron silicate and 15.2micron CO2 ice bands. Until recently, the 6.85micron band had only been detected towards embedded protostellar objects. Two additional quiescent dust sightlines from the C2D results now also indicate the 6.85micron band (Taurus and Serpens) by Knez et al. 2005, demonstrating the role of energetic processing within pristine ices prior to the onset of star formation.

Ennico, Kimberly↗

Radiolytic Cryovolcanism Revisited

Location of Enceladus within the inner magnetosphere of Saturn makes it likely that energetic electron irradiation, ion-neutral chemistry of the emergent cryovolcanic plume gas, and resultant radiolytic modification of surface ice composition could impact long-term evolution of molecular composition in the global ice crust. Thermally-driven convection of ice in the south polar terrain would bring radiolytic oxidant products into contact with subsurface reservoirs of primordial organics on million-year time scales. The chemical reactions leading to CO2 gas production as a primary gas-piston driver of cryovolcanic activity would be exponentially elevated in the warm-ice margins of a heated fluid. The fluid temperature is typically assumed to be below 273 K but could be much higher in a gas-pressurized deep subsurface environment. The Perrier Ocean model has demonstrated how a CO2-loaded fluid could account for the observed jets, while the heat content of the fluid arising from the moon's deeper interior could support high levels of chemical reactivity in the thermal margins. Since mass loss and tidal dissipation arguments do not support continuous activity over billions of years, the activity is likely very episodic so that even low-level energy sources including irradiation-driven radiolysis of surface ices could substantially contribute to the chemical dynamics of the activity apparently now in high phase. A multi-phase thermochemical model, and supporting laboratory measurements of temperature-dependent reaction rates, are needed to investigate these potentially complex processes.

Cooper, John F.↗

Giant-scale supernova remnants - The role of differential galactic rotation and the formation of molecular clouds

The evolution of remnants produced by the total supernova power from an evolved OB association in a differentially rotating galactic disk is presented. The calculations at 5 kpc and 10 kpc from the galactic center lead to column densities across the remnant shell, or across sections of the remnants, which eventually exceed the opacity criterion of Franco and Cox (1986) and thus form molecular clouds. The resultant clouds have masses larger than 100,000 solar masses, dimensions of several hundred parsecs, and a separation larger than 1 kpc. In contrast, at 20 kpc from the galactic center the opacity criterion is never fulfilled.

Tenorio-Tagle, G.↗

Oxygen evolution on a SrFeO3 anode - Mechanistic considerations from molecular orbital theory

Various pathways proposed in the literature for the evolution of O2 in electrochemical oxidations are explored using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory and the cluster models of the SrFeO3 surface as a prototype material. Calculations indicate that oxygen atoms can be easily formed on the (100) surface as well as on the edge cation sites of a SrFeO3 anode by the discharge of OH(-), followed by its deprotonation and electron transfer to the electrode. The O atoms can form O2 on the edge and corner sites, where the Fe(4+) is coordinated to four and three bulk oxygen anions, respectively. The calculations strongly disfavor mechanisms involving coupling of oxygen atoms adsorbed on different cations as well as a mechanism featuring an ozone intermediate.

Mehandru, S. P.↗

Chemical evolution of dense clouds

Attention is given to chemical processes which could determine the molecular composition of the cloud during the several stages of its evolution, taking into account thermal reactions at the relatively high interstellar densities expected during the processes. The origin of the observed molecules is discussed together with questions of molecular evolution during collapse of the cloud and the role of organic molecules in planetary chemical evolution. A number of experiments are also considered along with the application of the experimental results to cloud equilibrium problems.

Chapelle, E. W.↗

The role of the molecular-metallic transition of hydrogen in the evolution of Jupiter, Saturn, and brown dwarfs

An equation of state for hydrogen which predicts a molecular-metallic phase transition at finite temperatures has become available recently. The effect of this phase transition on the cooling histories of these two giant planets and of substellar brown dwarfs is studied. The phase transition alters the present age of Jupiter and of Saturn by a few percent. Interestingly, the cooling of brown dwarfs is most strongly affected at the time when the interior adiabat crosses the critical point of the phase transition.

Saumon, Didier↗

Interfacial Charge Transfer Pathways in Photoelectrochemical H 2 Evolution by a Single-Component Molecular Catalyst on a Conductive Metal Oxide

Dye-sensitized photoelectrosynthesis cells traditionally combine a photosensitizing dye to harvest light and a catalyst to generate chemical fuels on a semiconductor. Here, in this work, a photoactive catalyst capable of both light absorption and fuel formation, [Cp*Ir(4,4′-Y 2 -bpy)Cl][Cl] (Cp* = pentamethylcyclopentadienyl, bpy = 2,2′-bipyridine, Y = CH 2 PO 3 H 2 ), is anchored to a mesoporous tin-doped indium oxide (ITO) electrode and facilitates photoelectrochemical H 2 evolution in water without the need for additional photosensitizers or sacrificial reductants. Spectroelectrochemistry indicates a single-site H 2 evolution mechanism involving charge injection to ITO, in contrast to the bimetallic mechanism observed in solution. Cyclic voltammetry and variable-potential chronoamperometry under illumination probe competing pathways via interfacial electron transfer between the Ir hydride excited state and the conductive ITO electrode. A Marcus theory framework provides reorganization energies for competing interfacial electron transfer pathways from potential-dependent quantum yield measurements. The light-driven H 2 evolution catalysis on conducting oxide proceeds with high Faradaic efficiency and current densities comparable to photoelectrodes utilizing p-type semiconductors. By uncovering the principal electron transfer pathways that govern photocatalytic efficiency, this study establishes design principles for hybrid molecular photoelectrocatalysts.

catalysts↗

Dissociative recombination in interstellar clouds

Molecular ions play a significant role in the chemistry and evolution of interstellar molecular clouds, even though these regions are overwhelmingly neutral. The dissociative recombination (DR) process governs the abundances of many of these ions and of related neutral species. The gas-phase ion-molecule chemistry of the simplest species is summarized, with emphasis on those problems which are most sensitive to uncertain rates or product branching ratios of DR processes. Examples of the kinds of information needed about DR processes are presented. The importance of the H3(+) ion and prospects for its direct observation are discussed.

Black, John H.↗

Role of Amorphous Chains in Nanoplastic Formation from Semicrystalline Polymers

Semicrystalline polymers, e.g., polyethylene terephthalate (PET), release micro- (100 nm to 1 mm) and nanoplastics (up to 100 nm) [MNPL] when they are degraded under quiescent conditions. However, the exact molecular mechanisms leading to material fragmentation into MNPL are unknown. Here, we monitor the evolution of chain molecular weight and the MNPL production kinetics during hydrolysis of PET pellets. We find that only ~0.6% of the amorphous phase ester bonds are hydrolyzed at the onset of MNPL release. Then, by combining a random scission model with measured amorphous spacings, we estimate that only ~15% of the stress transmitters in the amorphous phase, namely, bridges and entangled loops, have failed by this point. Thus, spontaneous fragmentation of the semicrystalline nanostructure occurs despite significant intercrystalline connectivity. We resolve this apparent contradiction by proposing that fragmentation can only occur when progressive tie-chain scission causes the material to undergo the ductile/brittle transition. Mechanistically, we speculate that the internal stresses responsible for material fragmentation are caused by processing (i.e., residual stresses) and/or sample densification induced by chemi-crystallization. We discuss additional factors that may affect our analysis and thus require further investigation, such as skin-core effects, preferential degradation of stress transmitters and/or recrystallization processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interstellar processes; Proceedings of the Symposium, Grand Teton National Park, WY, July 1-7, 1986

The conference presents papers on the Milky Way as a galaxy; observations of components of the interstellar medium; interstellar magnetic properties; interstellar processes on a galactic scale; dynamical processes in interstellar clouds; interstellar dust grains; interstellar chemical processes; and heating, cooling, and radiative processes. Attention is given to H2 in the Galaxy, hot interstellar gas in the Galactic disk and halo, interstellar magnetic fields, cloud formation and destruction, theoretical approaches to interstellar turbulence, and infrared absorption and emission characteristics of interstellar PAHs. Other topics include gas phase chemical processes in molecular clouds, the chemical evolution of galaxies, and the atomic and molecular physics of interstellar heating and cooling.

Hollenbach, David J.↗

Contributions of experimental protobiogenesis to the theory of evolution

Inferences from experiments in protobiogenesis are examined as a forward extension of the theory of evolutionary biology. A nondiscontinuous, intraconsistent theory of general evolution embracing both protobiology and biology is outlined. This overview emphasizes Darwinian selection in the later stages of evolution, and stereochemical molecular selection in some of its earlier stages. It incorporates the concept of limitation of the scope of evolution by internal constraints on variation, based on the argument that internally limiting constraints observed in experiments with molecules are operative in organisms, if chemical processes occur within biological processes and biological processes are assumed to be exponentializations of chemical processes. Major evolutionary events might have occurred by rapid self-assembly processes analogous to those observed in the formation of phase-separated microspheres from amorphous powder or supersaturated solutions.

Fox, S. W.↗

Boundary Conditions for the Paleoenvironment: Chemical and Physical Processes in the Pre-Solar Nebula

The basic theme of this program is the study of molecular complexity and evolution in interstellar clouds and in primitive solar system objects. Research has included the detection and study of a number of new interstellar molecules and investigation of reaction pathways for astrochemistry from a comparison of theory and observed molecular abundances. The latter includes studies of cold, dark clouds in which ion-molecule chemistry should predominate, searches for the effects of interchange of material between the gas and solid phases in interstellar clouds, unbiased spectral surveys of particular sources, and systematic investigation of the interlinked chemistry and physics of dense interstellar clouds. In addition, the study of comets has allowed a comparison between the chemistry of such minimally thermally processed objects and that of interstellar clouds, shedding light on the evolution of the biogenic elements during the process of solar system formation.

Irvine, William M.↗