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Structural investigations of hydrogen cyanide polymers: new insights using TMAH thermochemolysis/GC-MS.

Hydrogen cyanide polymers form spontaneously from HCN and traces of base catalysts. It is probable that these polymers played an important role in the early stages of chemical evolution. Nevertheless, their full structural characterization has still not been accomplished. A number of mass spectrometric methods have now been applied to this structural problem including FAB-MS, thermal desorption EI-MS, ESI-MS, APCI-MS and off-line TMAH thermochemolysis/GC-MS. This latter method causes bond cleaveage and in situ methylation producing a suite of products which provides valuable insight into the substructural features of HCN polymers and also promises to serve as a sensitive diagnostic tool for detecting the presence of HCN polymers in samples from diverse sources.

Evolution, Chemical↗

Observation of indigenous polycyclic aromatic hydrocarbons in 'giant' carbonaceous antarctic micrometeorites.

Two-step laser desorption/laser ionization mass spectrometry (microL2 MS) was used to establish the nature and mass distribution of polycyclic aromatic hydrocarbons (PAHs) in fragments of fifteen 'giant' (approximately 200 microns) carbonaceous Antarctic micrometeorites (AMMs). Detectable concentrations of PAHs were observed in all AMMs showing a fine-grained matrix. The range of integrated PAH signal intensities varied between samples by over two orders of magnitude. No evidence of contamination whilst in the Antarctic environment could be found. The dramatic variation of both PAH signal intensities and mass distributions between AMMs along with comprehensive contamination checks demonstrates that particles are not exposed to terrestrial PAHs at or above detection limits, either subsequent, during or prior to collection. Comparison of the observed PAH distributions with those measured in three carbonaceous chondrites [Orgueil (CI1), Murchison (CM2) and Allende (CV3)] under identical conditions demonstrated that marked differences exist in the trace organic composition of these two sources of extraterrestrial matter. In general, AMMs show a far richer distribution of unalkylated 'parent' PAHs with more extended alkylation series (replacement of -H with -(CH2)n-H; n = 1, 2, 3 ...). The degree of alkylation loosely correlates with a metamorphic index that represents the extent of frictional heating incurred during atmospheric entry. A search for possible effects of the chemical composition of the fine-grain matrix of host particles on the observed PAH distributions reveals that high degrees of alkylation are associated with high Na/Si ratios. These results, in addition to other observations by Maurette, indicate that 'giant' micrometeorites survive hypervelocity (> or = 11 km s-1) atmospheric entry unexpectedly well. Because such micrometeorites are believed to represent the dominant mass fraction of extraterrestrial material accreted by the Earth, they may have played a significant role in the prebiotic chemical evolution of the early Earth through the delivery of complex organic matter to the surface of the planet.

Antarctic Regions↗

Prebiotic synthesis of nucleotides.

If an RNA-only world preceded more complex forms of life, then it is essential that the process whereby the first nucleotides were made be considered. Presumably there were no enzymes and no templates to facilitate the synthesis of the first nucleotides so another form of chemical evolution must have been involved. Answers to problems of this sort were sought vigorously in the 1960s and the early 1970s but many issues were left unresolved. Progress made in the last few years has added to this early work and brings us closer to a satisfactory solution. In this article key results, old and new, and some ideas as to how further progress is likely to be made are discussed. There are reasons for optimism. Substantial progress has been made on the synthesis of purines and ribose, phosphorylation and polyphosphorylation. The outstanding problems at this juncture relate to the synthesis of ribose to the exclusion of the other aldopentoses and to the problem of linking ribose to the purine bases.

Evolution, Chemical↗

Unusual stable isotope ratios in amino acid and carboxylic acid extracts from the Murchison meteorite.

Much effort has been directed to analyses of organic compounds in carbonaceous chondrites because of their implications for organic chemical evolution and the origin of life. We have determined the isotopic composition of hydrogen, nitrogen and carbon in amino acid and monocarboxylic acid extracts from the Murchison meteorite. The unusually high D/H and 15N/14N ratios in the amino acid fraction (delta D = 1,370% after correction for isotope exchange; delta 15N = 90) are uniquely characteristic of known interstellar organic materials. The delta D value of the monocarboxylic acid fraction is lower (377%), but still consistent with an interstellar origin. These results confirm the extraterrestrial origin of both classes of compound, and provide the first evidence suggesting a direct relationship between the massive organo-synthesis occurring in interstellar clouds and the presence of pre-biotic compounds in primitive planetary bodies. The isotope data also bear on the historical problem of distinguishing indigenous material from terrestrial contaminants.

Amino Acids↗

The organic content of the Tagish Lake meteorite.

The Tagish Lake meteorite fell last year on a frozen lake in Canada and may provide the most pristine material of its kind. Analyses have now shown this carbonaceous chondrite to contain a suite of soluble organic compounds (approximately 100 parts per million) that includes mono- and dicarboxylic acids, dicarboximides, pyridine carboxylic acids, a sulfonic acid, and both aliphatic and aromatic hydrocarbons. The insoluble carbon exhibits exclusive aromatic character, deuterium enrichment, and fullerenes containing "planetary" helium and argon. The findings provide insight into an outcome of early solar chemical evolution that differs from any seen so far in meteorites.

Amino Acids↗

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.

Amino Acids↗

A conceptual design for cosmo-biology experiments in Earth's Orbit.

A conceptual design was developed for a cosmo-biology experiment. It is intended to expose simulated interstellar ice materials deposited on dust grains to the space environment. The experimental system consists of a cryogenic system to keep solidified gas sample, and an optical device to select and amplify the ultraviolet part of the solar light for irradiation. By this approach, the long lasting chemical evolution of icy species could be examined in a much shorter time of exposure by amplification of light intensity. The removal of light at longer wavelength, which is ineffective to induce photochemical reactions, reduces the heat load to the cryogenic system that holds solidified reactants including CO as a constituent species of interstellar materials. Other major hardware components were also defined in order to achieve the scientific objectives of this experiment. Those are a cold trap maintained at liquid nitrogen temperature to prevent the contamination of the sample during the exposure, a mechanism to exchange multiple samples, and a system to perform bake-out of the sample exposure chamber. This experiment system is proposed as a candidate payload implemented on the exposed facility of Japanese Experiment Module on International Space Station.

Cold Temperature↗

Titan and exobiological aspects of the Cassini-Huygens mission.

Titan, the largest satellite of Saturn, has a dense N2-CH4 atmosphere rich in organic compounds, both in gas and in aerosol phases. Its surface is probably covered by oceans of liquid methane-ethane mixtures, with many dissolved organics. This quasi planet appears as a natural laboratory to study chemical evolution toward complex organic systems in a planetary environment over a long time scale. With the Cassini-Huygens mission NASA and ESA will jointly send an orbiter (Cassini) around Saturn and a probe (Huygens) in the atmosphere of Titan. This mission, currently planned to be launched in 1996-1997 for a Saturn - Titan arrival in 2004, offers a unique opportunity to study in detail extra-terrestrial organic processes. Consequently, it has important implications in the field of exobiology and the origins of life.

Aerosols↗

Titan and the origin of life on Earth.

The relevance of Titan to the study of pre-biotic chemistry and the origin of life on Earth will be addressed by an interdisciplinary group of Cassini/Huygens scientists using the different, but synergistic data sets obtained by NASA's Cassini Orbiter and ESA's Huygens Probe. Titan's special importance lies in the primitive chemically-reducing nature of its atmosphere Cassini/ Huygens instruments will determine what compounds form in this environment, and the results will be compared with models for pre-biological chemical evolution on Earth.

Atmosphere↗

Life and the outer planets. II. Enzyme activity in ammonia-water systems and other exotic media at various temperatures.

Enzyme activities are customarily measured in aqueous solutions. Activity and thermodynamic parameters are based upon behavior in these solutions although they in no way represent the highly structured internal surface system of the cell. Actual environmental limits for enzyme action may be greater than generally assumed. Peroxidase, catalase, urease and amylase retain activity in drastically modified aqueous and nonaqueous media, including aprotic solvents. Examples include formic acid, methanol, formamide, nitromethane, 10 M LiCl and 15 M aqueous ammonia. Temperatures as low as 225-233 degrees K permit activity in some media. Ammonia-rich environments are compatible with some forms of terrestrial life. Enzyme activity in these exotic media and conditions is relevant to chemical evolution on Jupiter and similar planetary systems.

Ammonia↗

The effect of ultraviolet light (PRK-2) on pentoses in the presence of various minerals.

4.0 X 10(-2) M solutions (pH 5.8) of ribose, arabinose and xylose were irradiated in UV light (1.84 X 10(9) erg cm-2 to 6.12 X 10(9) erg cm-2) in the presence of 5 mg/ml of Al2O3, SiO2, TiO2, V2O5, Cr2O3, Fe2O3, CuO, ZnO, schist and feldspar oxides. The resulting substance had an absorption spectrum with lambda max 245 nm and lambda min 288 nm. In the presence of all the oxides except that of V2O5 lambda max shifted to 265-268 nm. When irradiation was carried out in an alkaline medium (pH 10.0-11.0) containing no oxides the absorption band showed lambda max 265 nm as well. The photolysis was followed by the oxidative breakdown of pentoses resulting in the formation of H2CO, carbonyl substances, organic peroxides and acids. The quantum yield (phi) during photolysis without sensitizers for ribose, arabinose and xylose respectivelywas: phi (H2CO) - 2.32 X 10(-3), 1.99 X 10(-3), 1.69 X 10(-3) and phi (C=O) -1.58 X 10(-3), 1.46 X 10(-3), 1.43 X 10(-3). By the ability to sensitize formation of oxydation products of pentoses, the oxides are arranged as follows: Fe2O3 > or = V2O5 > or = TiO2 > or = SiO2 > Cr2O3 > CuO > pentose > or = ZnO. By their effect on phi (-m) of pentoses the oxides make up the sequence: Fe2O3 > or = TiO2 > or = V2O5 > or = SiO2 > feldspar > schist > Al2O3 > Cr2O3 > pentose > ZnO. By the increase of phi (-m) pentoses are arranged in a row: ribose (6.4 X 10(-3) > arabinose (2.5 X 10(-3)) > xylose (2.1 X 10(-3)). Photolysis in various gases has shown that oxidative destruction of pentoses increases according to: air > N2 > Ar. The results show that in the prebiological period on Earth, and possibly even at present on some other planets, various minerals could produce a photosensitizing effect on the breakdown of pentoses synthesized abiogenically from formaldehyde. Ribose proved to be the least resistant to photolysis. This fact is of interest in relation to studying the chemical evolution of carbohydrates and their interaction with purine and pyrimidine bases.

Arabinose↗

Evolution was chemically constrained.

The objective of this paper is to present a systems view of the major features of biological evolution based upon changes in internal chemistry and uses of cellular space, both of which it will be stated were dependent on the changing chemical environment. The account concerns the major developments from prokaryotes to eukaryotes, to multi-cellular organisms, to animals with nervous systems and a brain, and finally to human beings and their uses of chemical elements in space outside themselves. It will be stated that the changes were in an inevitable progression, and were not just due to blind chance, so that "random searching" by a coded system to give species had a fixed overall route. The chemical sequence is from a reducing to an ever-increasingly oxidizing environment, while organisms retained reduced chemicals. The process was furthered recently by human beings who have also increased the range of reduced products trapped on Earth in novel forms. All the developments are brought about from the nature of the chemicals which organisms accumulate using the environment and its changes. The relationship to the manner in which particular species (gene sequences) were coincidentally changed, the molecular view of evolution, is left for additional examination. There is a further issue in that the changes of the chemistry of the environment developed largely at equilibrium due to the relatively fast reactions there of the available inorganic chemicals. Inside cells, some of these same chemicals also came to equilibrium within compounds. All such equilibria reduced the variance (degrees of freedom) of the total environmental/biological system and its possible development. However, the more sophisticated organic chemistry, almost totally inside cells until humans evolved, is kinetically controlled and limited by the demands of cellular reduction necessary to produce essential chemicals and by the availability of certain elements and energy. Hence the variability of reductive cellular organic chemistry and its limitations in cells have to be considered separately. While as a whole they drive the oxidation of the environment, they also allow speciation within the major changes of organisms. Human beings have introduced recently new, virtually irreversible, inorganic and organic chemistry in the environment, much of it new modes of irreversible storage of reduced chemicals, and this is, we state, the last possible step of chemical evolution. We must attempt to evaluate its effect on organisms generally. It must be clear that all the changes and the original life forms are dependent upon energy as well as material capture and flow. We shall have to consider in which forms energy was available over the period of evolution, how it was usefully transformed, and the ways in which its sources changed.

Animals↗

Effect of hydrodynamic interactions on the evolution of chemically reactive ternary mixtures.

We investigate the structural evolution of an A/B/C ternary mixture in which the A and B components can undergo a reversible chemical reaction to form C. We developed a lattice Boltzmann model for this ternary mixture that allows us to capture both the reaction kinetics and the hydrodynamic interactions within the system. We use this model to study a specific reactive mixture in which C acts as a surfactant, i.e., the formation of C at the A/B interface decreases the interfacial tension between the A and B domains. We found that the dynamics of the system is different for fluids in the diffusive and viscous regimes. In the diffusive regime, the formation of a layer of C at the interface leads to a freezing of the structural evolution in the fluid; the values of the reaction rate constants determine the characteristic domain size in the system. In the viscous regime, where hydrodynamic interactions are important, interfacial reactions cause a slowing down of the domain growth, but do not arrest the evolution of the mixture. The results provide guidelines for controlling the morphology of this complex ternary fluid.

Journal Article↗

Radioactivity as a significant energy source in prebiotic synthesis.

Radioactivity in the continental crust (due mainly to the isotopes 238U, 235U, 232Th and 40K), as a energy source for chemical evolution in the early Archean (between 3.5 and approximately 4 Ga bp), is reviewed. The most important radioactive source in the continental crust is due to the production and accumulation of radioactive gases within the crust voids (porosity). The study of such mechanism has allowed us to reach a deeper understanding about the nature of the radioactive source and to describe its behavior, particularly with regard to prebiotic chemical evolution. An effective total energy of 3 x 10(18) Ja-1 has been obtained for a depth of 1 km, 4 Ga ago. If a depth of 30 km is taken, the obtained value is almost equal to the UV solar energy radiation (lambda < 150 nm). Within the voids the radioactive source of the continental crust played a relevant role in prebiotic synthesis. In uranium deposits of the same age, the role of radioactivity must have been even more relevant in favoring chemical evolution.

Earth, Planet↗

Convergent evolution of chemical defense in poison frogs and arthropod prey between Madagascar and the Neotropics.

With few exceptions, aposematically colored poison frogs sequester defensive alkaloids, unchanged, from dietary arthropods. In the Neotropics, myrmicine and formicine ants and the siphonotid millipede Rhinotus purpureus are dietary sources for alkaloids in dendrobatid poison frogs, yet the arthropod sources for Mantella poison frogs in Madagascar remained unknown. We report GC-MS analyses of extracts of arthropods and microsympatric Malagasy poison frogs (Mantella) collected from Ranomafana, Madagascar. Arthropod sources for 11 "poison frog" alkaloids were discovered, 7 of which were also detected in microsympatric Mantella. These arthropod sources include three endemic Malagasy ants, Tetramorium electrum, Anochetus grandidieri, and Paratrechina amblyops (subfamilies Myrmicinae, Ponerinae, and Formicinae, respectively), and the pantropical tramp millipede R. purpureus. Two of these ant species, A. grandidieri and T. electrum, were also found in Mantella stomachs, and ants represented the dominant prey type (67.3% of 609 identified stomach arthropods). To our knowledge, detection of 5,8-disubstituted (ds) indolizidine iso-217B in T. electrum represents the first izidine having a branch point in its carbon skeleton to be identified from ants, and detection of 3,5-ds pyrrolizidine 251O in A. grandidieri represents the first ponerine ant proposed as a dietary source of poison frog alkaloids. Endemic Malagasy ants with defensive alkaloids (with the exception of Paratrechina) are not closely related to any Neotropical species sharing similar chemical defenses. Our results suggest convergent evolution for the acquisition of defensive alkaloids in these dietary ants, which may have been the critical prerequisite for subsequent convergence in poison frogs between Madagascar and the Neotropics.

Alkaloids↗

Prebiotic phosphorus chemistry reconsidered.

The available evidence indicates that the origin of life on Earth certainly occurred earlier than 3.5 billion years ago and perhaps substantially earlier. The time available for the chemical evolution which must have preceded this event is more difficult to estimate. Both endogenic and exogenic contributions to chemical evolution have been considered; i.e., from chemical reactions in a primitive atmosphere, or by introduction in the interiors of comets and/or meteorites. It is argued, however, that the phosphorus chemistry of Earth's earliest hydrosphere, whether primarily exogenic or endogenic in origin, was most likely dominated by compounds less oxidized than phosphoric acid and its esters. A scenario is presented for the early production of a suite of reactive phosphonic acid derivatives, the properties of which may have foreshadowed the later appearance of biophosphates.

Atmosphere↗

Amplification of diverse catalytic properties of evolving molecules in a simulated hydrothermal environment.

We observed chemical evolution in a mixture of four amino acids, glycine, L-alanine, L-valine and L-aspartic acid, circulated through a flow reactor simulating the thermodynamic conditions of a hydrothermal environment. These monomers form peptides with tertiary structures and potential catalytic functions. The HPLC profile of synthesized oligomers varied with each particular run, but the products were found to separate into distinct clusters when more than one hundred runs were compared statistically. This observation suggests that chemical evolution on the early Earth had stochastic aspects that must be understood in order to develop useful models of prebiotic evolution.

Alanine↗

Organic matter in meteorites.

Some primitive meteorites are carbon-rich objects containing a variety of organic molecules that constitute a valuable record of organic chemical evolution in the universe prior to the appearance of microorganisms. Families of compounds include hydrocarbons, alcohols, aldehydes, ketones, carboxylic acids, amino acids, amines, amides, heterocycles, phosphonic acids, sulfonic acids, sugar-related compounds and poorly defined high-molecular weight macromolecules. A variety of environments are required in order to explain this organic inventory, including interstellar processes, gas-grain reactions operating in the solar nebula, and hydrothermal alteration of parent bodies. Most likely, substantial amounts of such organic materials were delivered to the Earth via a late accretion, thereby providing organic compounds important for the emergence of life itself, or that served as a feedstock for further chemical evolution. This review discusses the organic content of primitive meteorites and their relevance to the build up of biomolecules.

Evolution, Chemical↗