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At least 163 records · Page 9

Rates of Decomposition of Ribose and other Sugars: Implications for Chemical Evolution

The existence of the RNA world, in which RNA acted as a catalyst as well as an informational macromolecule, assumes a large prebiotic source of ribose or the existence of pre-RNA molecules with backbones different from ribose-phosphate. The generally accepted prebiotic synthesis of ribose, the formose reaction, yields numerous sugars without any selectivity. Even if there were a selective synthesis of ribose, there is still the problem of stability. Sugars are known to be unstable in strong acid or base, but there are few data for neutral solutions. Therefore, we have measured the rate of decomposition of ribose between pH 4 and pH 8 from 40 C to 120 C. The ribose half-lives are very short (73 min at pH 7.0 and 100 C and 44 years at pH 7.0 and 0 C). The other aldopentoses and aldohexoses have half-lives within an order of magnitude of these values, as do 2-deoxyribose, ribose 5-phosphate, and ribose 2,4bisphosphate. These results suggest that the backbone of the first genetic material could not have contained ribose or other sugars because of their instability.

Larralde, Rosa↗

Calculating Chemical Evolution on the Web

We have constructed an interactive web site that may be of interest to cosmochemists seeking to understand the evolution of isotopes in the Galaxy. The URL is http://photon.phys.clemson.edu/gce.html. Additional information is contained in the original extended abstract.

Meyer, B. S.↗

Chemical evolution and the origin of life: bibliography supplement 1985

This bibliography is the seventeenth annual supplement to the comprehensive bibliography on the same subject which was published in Space Life Sci. 2(1970), 225-295; 3(1972), 293-304; 4(1973), 309-329 and in Origins of Life 5(1974), 505-527; 6(1975), 285-300; 7(1976), 75-85; 8(1977), 59-66; 9(1978), 67-74; 10(1980), 69-87; 10(1980), 379-404; 11(1981), 273-288; 12(1982), 93-118; 13(1983), 61-80; 15(1984), 55-69; 17(1987), 171-184; 17(1987), 185-206.

NASA Program Exobiology↗

Xenia: A Probe of Cosmic Chemical Evolution

Xenia is a concept study for a medium-size astrophysical cosmology mission addressing the Cosmic Origins key objective of NASA's Science Plan. The fundamental goal of this objective is to understand the formation and evolution of structures on various scales from the early Universe to the present time (stars, galaxies and the cosmic web). Xenia will use X-and y-ray monitoring and wide field X-ray imaging and high-resolution spectroscopy to collect essential information from three major tracers of these cosmic structures: the Warm Hot Intergalactic Medium (WHIM), Galaxy Clusters and Gamma Ray Bursts (GRBs). Our goal is to trace the chemo-dynamical history of the ubiquitous warm hot diffuse baryon component in the Universe residing in cosmic filaments and clusters of galaxies up to its formation epoch (at z =0-2) and to map star formation and galaxy metal enrichment into the re-ionization era beyond z ~ 6. The concept of Xenia (Greek for "hospitality") evolved in parallel with the Explorer of Diffuse Emission and GRB Explosions (EDGE), a mission proposed by a multinational collaboration to the ESA Cosmic Vision 2015. Xenia incorporates the European and Japanese collaborators into a U.S. led mission that builds on the scientific objectives and technological readiness of EDGE.

Kouveliotou, Chryssa↗

Chemical Evolution in the Interstellar Medium: From Astrochemistry to Astrobiology

Great strides have been made in our understanding of interstellar material thanks to advances in infrared astronomy and laboratory astrophysics. Ionized polycyclic aromatic hydrocarbons (PAHs), shockingly large molecules by earlier astrochemical standards, are widespread and very abundant throughout much of the Universe. In cold molecular clouds, the birthplace of planets and stars, interstellar molecules freeze onto dust and ice particles forming mixed molecular ices dominated by simple species such as water, methanol, ammonia, and carbon monoxide. Within these clouds, and especially in the vicinity of star and planet forming regions, these ices and PAHs are processed by ultraviolet light and cosmic rays forming hundreds of far more complex species, some of biogenic interest. Eventually, these are delivered to primordial planets by comets and meteorites. Astrochemical evolution, highlights of this field from a chemist's perspective, and the astronomer's infrared toolbox will be reviewed.

Allamandola, Louis J.↗

Layered Model for Radiation-Induced Chemical Evolution of Icy Surface Composition and Dynamics on Kuiper Belt and Oort Cloud Bodies

The diversity of albedos and surface colors on observed Kuiper Belt and Inner Oort Cloud objects remains to be explained in terms of competition between primordial intrinsic versus exogenic drivers of surface and near-surface evolution. Earlier models have attempted without success to attribute this diversity to the relations between surface radiolysis from cosmic ray irradiation and gardening by meteoritic impacts. A more flexible approach considers the different depth-dependent radiation profiles produced by low-energy plasma, suprathermal, and maximally penetrating charged particles of the heliospheric and local interstellar radiation environment. Generally red objects of the dynamically cold (low inclination, circular orbit) Classical Kuiper Belt might be accounted for from erosive effects of plasma ions and reddening effects of high energy cosmic ray ions, while suprathermal keV-MeV ions could alternatively produce more color neutral surfaces. The deepest layer of more pristine ice can be brought to the surface from meter to kilometer depths by larger impact events and potentially by cryovolcanic activity. The bright surfaces of some larger objects, e.g. Eris, suggest ongoing resurfacing activity. Cycles of atmospheric formation and surface freezeout can further account for temporal variation as observed on Pluto. The diversity of causative processes must therefore be understood to account for observationally apparent diversities of the object surfaces.

Cooper, John F.↗

A Fly-Through Mission Strategy Targeting Peptide as a Signature of Chemical Evolution and Possible Life in Enceladus Plumes

In situ detection of organic molecules in the extraterrestrial environment provides a key step towards better understanding the variety and the distribution of building blocks of life and it may ultimately lead to finding extraterrestrial life within the Solar System. Here we present combined results of two separate experiments that enable us to realize such in situ life signature detection from the deep habitats of the "Ocean World": a hydrothermal reactor experiment simulating complex organic synthesis and a simulated fly-through capture experiment of organic-bearing microparticles using silica aerogels, followed by subsequent analysis. Both experiments employ peptide as a plausible organics existing in Encleadus plume particles produced in its subsurface ocean. Recent laboratory hydrothermal experiments and a theoretical model on silica saturation indicated an on going hydrothermal reactions in subsurface Enceladus ocean. Given the porous chondritic origin of the core, it is likely that organic compounds originated by radiation chemistry such as amino acid precursors could have been provided, leached, and altered through widespread water-rock interactions. By using the same laboratory experimental setup from the latest water-rock interaction study, we performed amino acid polymerization experiments for 144 days and monitored the organic complexity changing over time. So far over 3,000 peaks up to the size of greater than 600 MW were observed through the analysis of capillary electrophoresis time-of-flight mass spectrometry (CE-TOF-MS) with an indication of amino acid derivatives and short peptides. Generally abiotic polymerization of enantiomeric amino acids results in forming stereoisomeric peptides with identical molecular weight and formula as opposed to homochiral biopolymers. Assuming Enceladus plume particles may contain a mixture of stereoisomeric peptides, we were able to distinguish 16 of the 17 stereoisomeric tripeptides as a test sample using capillary electrophoresis (CE) under optimized conditions. We further conducted Enceladus plume fly-through capture experiment by accelerating peptides soaked in rock particles up to a speed of 5.7 km/s and capturing with originally developed hydrophobic silica aerogels. Direct peptide extraction with acetonitrile-water followed by CE analysis led to detection of only but two stereoisomeric acidic peptide peaks, presenting the first run-through hypervelocuty impact sample analysis targeting peptides as key molecule to to understand the ongoing astrobiology on Enceladus.

organic molecules↗

Ryugu Asteroid Sample Return Provides A Natural Laboratory for Primordial Chemical Evolution

The samples returned from near-Earth asteroid (162173) Ryugu provide a pristine record of the 4.6 billion years since the birth of the Solar System. The Hayabusa2 initial analysis team has integrated a range of analytical techniques to investigate Ryugu’s organic chemistry. Here, we highlight their latest findings, the potential questions which may be answered, and provide an overview of new prospects in the decade to come.

Asteroids↗

Simulating the evolution of the chemical composition of the 1988/89 winter vortex

During the 1988/89 Airborne Arctic Stratospheric Expedition (AASE) observations of the chemical composition and aerosol characteristics of the winter vortex were obtained from a NASA ER-2 aircraft. In this paper we present interpretations of observations obtained on three ER-2 flights using a Lagrangian coupled photochemical-microphysical model. It is argued that observations obtained on Jaunary 16 and 19, and February 10, represent different stages of the chemical evolution of the vortex, from the early stages of chlorine release, the onset of denitrification and the intensively processed state.

Jones, R. L.↗

Mineral catalysis of a potentially prebiotic aldol condensation

Minerals may have played a significant role in chemical evolution. In the course of investigating the chemistry of phosphonoacetaldehyde (PAL), an analogue of glycolaldehyde phosphate, we have observed a striking case of catalysis by the layered hydroxide mineral hydrotalcite ([Mg2Al(OH)6][Cl.nH2O]). In neutral or moderately basic aqueous solutions, PAL is unreactive even at a concentration of 0.1 M. In the presence of a large excess of NaOH (2 M), the compound undergoes aldol condensation to produce a dimer containing a C3-C4 double-bond. In dilute neutral solutions and in the presence of the mineral, however, condensation takes place rapidly, to produce a dimer which is almost exclusively the C2-C3 unsaturated product.

Non-NASA Center↗

Preference for internucleotide linkages as a function of the number of constituents in a mixture

Phosphoimidazolide-activated ribomononucleotides (*pN; see Scheme I) are useful substrates for the nonenzymatic synthesis of oligonucleotides. In the presence of metal ions dilute neutral aqueous solutions of *pN (0.01 M) typically yield only small amounts of dimers and traces of oligomers; most of *pN hydrolyzes to yield nucleoside 5'-monophosphate (5'NMP). An earlier investigation of *pN reactions in highly concentrated aqueous solutions (up to 1.4 M) showed, as expected, that the percentage yield of the condensation products increases and the yield of the hydrolysis product correspondingly decreases with *pN concentration (Kanavarioti 1997). Here we report product distributions in reactions with one, two, or three reactive components at the same total nucleotide concentration. *pN used as substrates were the nucleoside 5'-phosphate 2-methylimidazolides, 2-MeImpN, with N = cytidine (C), uridine (U), or guanosine (G). Reactions were conducted as self-condensations, i. e., one nucleotide only, with two components in the three binary U,C, U,G, and C,G mixtures, and with three components in the ternary U,C, G mixture. The products are 5'NMP, 5',5'-pyrophosphate-, 2',5'-, 3', 5'-linked dimers, cyclic dimers, and a small percentage of longer oligomers. The surprising finding was that, under identical conditions, including the same total monomer concentration, the product distribution differs substantially from one reaction to another, most likely due to changing intermolecular interactions depending on the constituents. Even more unexpected was the observed trend according to which reactions of the U,C,G mixture produce the highest yield of internucleotide-linked dimers, whereas the self-condensations produce the least and the reactions with the binary mixtures produce yields that fall in between. What is remarkable is that the approximately two-fold increase in the percentage yield of internucleotide-linked dimers is not due to a concentration effect or a catalyst, but to the increased complexity of the system from a single to two and three components. These observations, perhaps, provide an example of how increased complexity in relatively simple chemical systems leads to organization of the material and consequently to chemical evolution. A possible link between prebiotic chemistry and the postulated RNA world is discussed.

NASA Discipline Exobiology↗

Enantiomeric excesses in meteoritic amino acids

Gas chromatographic-mass spectral analyses of the four stereoisomers of 2-amino-2,3-dimethylpentanoic acid (dl-alpha-methylisoleucine and dl-alpha-methylalloisoleucine) obtained from the Murchison meteorite show that the L enantiomer occurs in excess (7.0 and 9.1%, respectively) in both of the enantiomeric pairs. Similar results were obtained for two other alpha-methyl amino acids, isovaline and alpha-methylnorvaline, although the alpha hydrogen analogs of these amino acids, alpha-amino-n-butyric acid and norvaline, were found to be racemates. With the exception of alpha-amino-n-butyric acid, these amino acids are either unknown or of limited occurrence in the biosphere. Because carbonaceous chondrites formed 4.5 billion years ago, the results are indicative of an asymmetric influence on organic chemical evolution before the origin of life.

NASA Program Exobiology↗

Impact contribution of prebiotic reactants to Earth

A study was performed to explore the effectiveness of comets for chemical evolution. The concentration of amino acids in various terrestrial environments was mathematically explored as there is evidence that amino acids formed as a result of cometary impact. First, the initial concentration of amino acids in surface environment after cometary impact was estimated. The effect of hydrothermal vents, ultra-violet rays, and clays was taken into consideration. Next, the absorption of amino acids by clay particles before degradation by ultra-violet light was analyzed. Finally, the effectiveness of clays, ultra-violet, and hydrothermal vents as sinks for cometary amino acids was compared. A mathematical model was then developed for the production of impact deposits on Earth for the past 2 Ga, and the relative thickness distribution was computed for impact deposits produced in 2 Ga. The reported relative thickness distribution of tillites and diamicites of all ages agrees with the thickness calculated from this impact model. This suggests that many of the ancient tillites and diamicites could be of impact origin. The effectiveness of comets was explored on the chemical evolution of amino acids. The effect of sinks such as clays, submarine vents, and UV light on amino acid concentration was considered. Sites favorable to chemical evolution of amino acids were examined, and it was concluded that chemical evolution could have occurred at or above the surface even during periods of intense bombardment of the Earth more than 3.8 billion years ago.

Aggarwal, Hans R.↗

Prebiotic organic syntheses and the origin of life

The outline of a modern paradigm for the origins of life on earth was first formulated by Oparin (1924). According to the considered hypothesis, living organisms arose naturally on the primitive earth through a lengthy process of chemical evolution of organic matter which began in the atmosphere and culminated in the primordial seas. Details regarding the chemical evolution paradigm are discussed, and chemical evolutionary processes formulated by principal contributors are reviewed in a historical context. Attention is given to the Oparin model of the prebiotic earth, the Urey model, the Rubey model, a multistage model for early atmospheric evolution, and other variations on the theme of prebiotic atmospheres. Evidence in support of the chemical evolution paradigm is considered along with modern models regarding the accretion of earth and the formation of its core, and problems and prospects for future studies.

Chang, S.↗