Showing papers in "Origins of Life and Evolution of Biospheres in 1999"

Lipid synthesis under hydrothermal conditions by Fischer-Tropsch-type reactions.

Abstract: Ever since their discovery in the late 1970's, mid-ocean-ridge hydrothermal systems have received a great deal of attention as a possible site for the origin of life on Earth (and environments analogous to mid-ocean-ridge hydrothermal systems are postulated to have been sites where life could have originated or Mars and elsewhere as well) Because no modern-day terrestrial hydrothermal systems are free from the influence of organic compounds derived from biologic processes, laboratory experiments provide the best opportunity for confirmation of the potential for organic synthesis in hydrothermal systems Here we report on the formation of lipid compounds during Fischer-Tropsch-type synthesis from aqueous solutions of formic acid or oxalic acid Optimum synthesis occurs in stainless steel vessels by heating at 175 degrees C for 2-3 days and produces lipid compounds ranging from C2 to > C35 which consist of n-alkanols, n-alkanoic acids, n-alkenes, n-alkanes and alkanones The precursor carbon sources used are either formic acid or oxalic acid, which disproportionate to H2, CO2 and probably CO Both carbon sources yield the same lipid classes with essentially the same ranges of compounds The synthesis reactions were confirmed by using 13C labeled precursor acids

Clay-nucleic acid complexes: characteristics and implications for the preservation of genetic material in primeval habitats.

Abstract: The equilibrium adsorption of three nucleic acids: chromosomal DNA, supercoiled plasmid DNA, and 25S rRNA, on the clay minerals, montmorillonite (M) and kaolinite (K), were studied. Adsorption of the nucleic acid on the clays was rapid and maximal after 90 min of contact time. Chromosomal DNA was adsorbed to a greater extent than plasmid DNA and RNA, and the adsorption was also greater on M than on K. Adsorption isotherms were of the L type, and a plateau was reached with all the complexes, with the exception of chromosomal DNA adsorbed on M. To determine where nucleic acids are adsorbed on clay minerals and the nature of the interaction, complexes were studied by X-ray diffraction (X-RD), electron microscopy, and Fourier transform infrared (FT-IR) spectroscopy. X-RD showed that nucleic acids did not penetrate the clay, indicating that the adsorption occurred primarily on the external surfaces of clay particles, as also suggested by electron microscopy observations. FT-IR spectra of clay-tightly bound nucleic acid complexes showed absorption bands that indicate a variation of the nucleic acids status as a consequence of their adsorption on clay. Data obtained suggested that the formation of clay-nucleic acid complex could have an important role in the preservation of genetic material in primeval habitats.

Habitability of planets around red dwarf stars.

Abstract: Recent models indicate that relatively moderate climates could exist on Earth-sized planets in synchronous rotation around red dwarf stars. Investigation of the global water cycle, availability of photosynthetically active radiation in red dwarf sunlight, and the biological implications of stellar flares, which can be frequent for red dwarfs, suggests that higher plant habitability of red dwarf planets may be possible.

Energetics and kinetics of the prebiotic synthesis of simple organic acids and amino acids with the FeS-H2S/FeS2 redox couple as reductant.

Abstract: The thermodynamics of the FeS-H2S/FeS2 redox couple and a select number of reactions critical to the synthesis of simple carboxylic acids and amino acids have been evaluated as a function of temperature This thermodynamic evaluation shows that the reducing power of the FeS-H2S/FeS2 redox couple decreases drastically with temperature By contrast the equilibria describing the reduction of CO2 and the formation of simple carboxylic acids and amino acids require an increasingly higher reducing power with temperature Given these two opposite trends, the thermodynamic driving force for CO2 reduction and amino acid formation with the FeS-H2S/FeS2 redox couple as reductant diminishes with increasing temperature An evaluation of the mechanism of CO2 reduction by the FeS-H2S/FeS2 couple suggests that the electron transfer from pyrrhotite to CO2 is hindered by a high activation energy, even though the overall reaction is thermodynamically favorable By comparison the electron transfer from pyrrhotite to either CS2, CO, or HCOOH are far more facile This theoretical analysis explains the results of experimental work by Keefe et al (1995), Heinen and Lauwers (1996) and Huber and Wachtershauser (1997) The implication is that a reaction sequence involving the reduction of CO2 with the FeS-H2S/FeS2 couple as reductant is unlikely to initiate a proposed prebiotic carbon fixation cycle (Wachtershauser, 1988b; 1990b, 1990a, 1992, 1993)

Silica, alumina and clay catalyzed peptide bond formation: enhanced efficiency of alumina catalyst.

Abstract: Catalytic efficiencies of clay (hectorite), silica and alumina were tested in peptide bond formation reactions of glycine (Gly), alanine (Ala), proline (Pro), valine (Val) and leucine (Leu). The reactions were performed as drying/wetting (hectorite) and temperature fluctuation (silica and alumina) experiments at 85 °C. The reactivity of amino acids decreased in order Gly > Ala > Pro ≈ Val ≈ Leu. The highest catalytic efficiency was observed for alumina, the only catalyst producing oligopeptides in all investigated reaction systems. The peptide bond formation on alumina is probably catalyzed by the same sites and via similar reaction mechanisms as some alumina-catalyzed dehydration reactions used in industrial chemistry.

Molecular distribution of monocarboxylic acids in Asuka carbonaceous chondrites from Antarctica.

Abstract: Molecular distribution of low-molecular-weight monocarboxylic acids was studied in three CM2 Asuka carbonaceous chondrites (A-881280, A-881334 and A-881458), which were recovered from Antarctica by the 29th Japanese Antarctic Research Expedition in 1988 GC and GC/MS analyses identified more than 30 monocarboxylic acids in A-881458, including aliphatic and aromatic acids with various structural isomers Isomeric phenolic compounds were also identified The aliphatic carboxylic acids have straight-chain structures having 2 to 12 carbon atoms (C2 to C12), and branched-chain structures (C4 to C9) The quantities of straight-chain acids decrease logarithmically with increasing carbon number At the same carbon number, a straight-chain isomer is always predominant compared to branched-chain isomers All of the 14 possible C4, C5 and C6 aliphatic monocarboxylic acids (not including optical isomers) have been identified, although all the isomers were not reported in Murchison and Y-791198 meteorites Of the 17 possible isomeric C7 acids, at least 14 isomers were tentatively identified by mass spectra (EI and CI mode) At C8 or above, peaks of branched-chain isomers become obscure, probably due to the large number of isomers and small concentrations Branched-chain monocarboxylic acids over C6 have never been reported in Murchison Although occurrence of aliphatic acids are similar between A-881458 and Murchison at C4, C5 and C6 acids, a major difference is that A-881458 as well as Y-791198 have straight- chain predominance among isomers in contrast to Murchison being branched-chain predominant In the case of isomeric aromatic compounds such as toluic acids and cresols, m-toluic acid and p-cresol are more abundant among their isomers, respectively The molecular distribution may not reflect thermodynamic equilibrium but rather a kinetically controlled process for their formation mechanism The other two CM2 chondrites (A-881280 and A-881334) were depleted in carboxylic acids in spite of similar carbon contents The depletion is not due to weathering on ice, because the degrees of weathering are small and similar among the three chondrites Probably those latter two chondrites may have been subjected to aqueous alteration or metamorphism on their meteorite parent bodies

Peroxide-modified titanium dioxide: a chemical analog of putative Martian soil oxidants.

Abstract: Hydrogen peroxide chemisorbed on titanium dioxide (peroxide-modified titanium dioxide) is investigated as a chemical analog to the putative soil oxidants responsible for the chemical reactivity seen in the Viking biology experiments. When peroxide-modified titanium dioxide (anatase) was exposed to a solution similar to the Viking labeled release (LR) experiment organic medium, CO2 gas was released into the sample cell headspace. Storage of these samples at 10 degrees C for 48 hr prior to exposure to organics resulted in a positive response while storage for 7 days did not. In the Viking LR experiment, storage of the Martian surface samples for 2 sols (approximately 49 hr) resulted in a positive response while storage for 141 sols essentially eliminated the initial rapid release of CO2. Heating the peroxide-modified titanium dioxide to 50 degrees C prior to exposure to organics resulted in a negative response. This is similar to, but not identical to, the Viking samples where heating to approximately 46 degrees C diminished the response by 54-80% and heating to 51.5 apparently eliminated the response. When exposed to water vapor, the peroxide-modified titanium dioxide samples release O2 in a manner similar to the release seen in the Viking gas exchange experiment (GEx). Reactivity is retained upon heating at 50 degrees C for three hours, distinguishing this active agent from the one responsible for the release of CO2 from aqueous organics. The release of CO2 by the peroxide-modified titanium dioxide is attributed to the decomposition of organics by outer-sphere peroxide complexes associated with surface hydroxyl groups, while the release of O2 upon humidification is attributed to more stable inner-sphere peroxide complexes associated with Ti4+ cations. Heating the peroxide-modified titanium dioxide to 145 degrees C inhibited the release of O2, while in the Viking experiments heating to this temperature diminished but did not eliminated the response. Although the thermal stability of the titanium-peroxide complexes in this work is lower than the stability seen in the Viking experiments, it is expected that similar types of complexes will form in titanium containing minerals other than anatase and the stability of these complexes will vary with surface hydroxylation and mineralogy.

Chemical reduction of phosphate on the primitive earth.

Abstract: If phosphorus played a role in the origin of life, some means of concentrating micromolar levels of phosphate (derived from the calcium phosphate mineral apatite), must first have been available. Here we show that simulated (mini)lightning discharges in model prebiotic atmospheres, including only minimally reducing ones, reduce orthophosphates, including apatite, to produce substantial yields of phosphite. Electrical discharges associated with volcanic eruptions could have provided a particularly suitable environment for this process. Production of relatively soluble and reactive phosphite salts could have supplied a pathway by which the first phosphorus atoms were incorporated into (pre)biological systems.

The combination of salt induced peptide formation reaction and clay catalysis: a way to higher peptides under primitive earth conditions.

Abstract: Two reactions with suggested prebiotic relevance for peptide evolution, the saltinduced peptide formation reaction and the peptide chain elongation/stabilization on clay minerals have been combined in experimental series starting from dipeptides and dipeptide/amino acid mixtures. The results show that both reactions can take place simultaneously in the same reaction environment and that the presence of mineral catalysts favours the formation of higher oligopeptides. These findings lend further support to the relevance of these reactions for peptide evolution on the primitive earth. The detailed effects of the specific clay mineral depend both on the nature of the mineral and the reactants in solution.

Autocatalytic synthesis of oligoglycine in a simulated submarine hydrothermal system.

Abstract: A flow reactor simulating a submarine hydrothermal system was constructed for examining the likelihood of oligopeptide synthesis from amino acids alone without recourse to any of condensing agents, templates or metallic ions. We demonstrated that when the initial reactant is glycine, the flow reactor can synthesize both di- and tri-glycine. The initial buildup of the yields of both the oligopeptides was found to be exponential with the elapse of time. The oligopeptide synthesis from glycine in the flow reactor could be autocatalytic.

Formation of glycolaldehyde phosphate from glycolaldehyde in aqueous solution.

Abstract: Amidotriphosphate (0.1 M) in aqueous solution at near neutral pH in the presence of magnesium ions (0.25 M) converts glycolaldehyde (0.025 M) within days at room temperature into glycolaldehyde phosphate in (analytically) nearly quantitative yields (76% in isolated product). This robust phosphorylation process was observed to proceed at concentrations as low as 30 microM glycolaldehyde and 60 microM phosphorylation reagent under otherwise identical conditions. In sharp contrast, attempts to achieve a phosphorylation of glycolaldehyde with cyclotriphosphate ('trimetaphosphate') as phosphorylating reagent were unsuccessful. Mechanistically, the phosphorylation of glycolaldehyde with amidotriphosphate is an example of intramolecular delivery of the phosphate group.

Did Viking discover life on Mars

Abstract: A major argument in the claim that life had been discovered during the Viking mission to Mars is that the results obtained in the Labeled Release (LR) experiment are analogous to those observed with terrestrial microorganisms. This assertion is critically examined and found to be implausible.

Clay catalysis of oligonucleotide formation: kinetics of the reaction of the 5'-phosphorimidazolides of nucleotides with the non-basic heterocycles uracil and hypoxanthine.

Abstract: The montmorillonite clay catalyzed condensation of activated monocleotides to oligomers of RNA is a possible first step in the formation of the proposed RNA world. The rate constants for the condensation of the phosphorimidazolide of adenosine were measured previously and these studies have been extended to the phosphorimidazolides of inosine and uridine in the present work to determine of substitution of neutral heterocycles for the basic adenine ring changes the reaction rate or regioselectivity. The oligomerization reactions of the 5'-phosphoromidazolides of uridine (ImpU) and inosine (ImpI) on montmorillonite yield oligo(U)s and oligo(I)s as long as heptamers. The rate constants for oligonucleotide formation were determined by measuring the rates of formation of the oligomers by HPLC. Both the apparent rate constants in the reaction mixture and the rate constants on the clay surface were calculated using the partition coefficients of the oligomers between the aqueous and clay phases. The rate constants for trimer formation are much greater than those dimer synthesis but there was little difference in the rate constants for the formation of trimers and higher oligomers. The overall rates of oligomerization of the phosphorimidazolides of purine and pyrimidine nucleosides in the presence of montmorillonite clay are the same suggesting that RNA formed on the primitive Earth could have contained a variety of heterocyclic bases. The rate constants for oligomerization of pyrimidine nucleotides on the clay surface are significantly higher than those of purine nucleotides since the pyrimidine nucleotides bind less strongly to the clay than do the purine nucleotides. The differences in the binding is probably due to Van der Waals interactions between the purine bases and the clay surface. Differences in the basicity of the heterocyclic ring in the nucleotide have little effect on the oligomerization process.

The fidelity of template-directed oligonucleotide ligation and the inevitability of polymerase function.

Abstract: The first living systems may have employed template-directed oligonucleotide ligation for replication. The utility of oligonucleotide ligation as a mechanism for the origin and evolution of life is in part dependent on its fidelity. We have devised a method for evaluating ligation fidelity in which ligation substrates are selected from random sequence libraries. The fidelities of chemical and enzymatic ligation are compared under a variety of conditions. While reaction conditions can be found that promote high fidelity copying, departure from these conditions leads to error-prone copying. In particular, ligation reactions with shorter oligonucleotide substrates are less efficient but more faithful. These results support a model for origins in which there was selective pressure for template-directed oligonucleotide ligation to be gradually supplanted by mononucleotide polymerization.

Mineral induced formation of pentose-2,4-bisphosphates.

Abstract: Formation of rac.-pentose-2,4-bisphosphates is demonstrated, starting from glycolaldehyde phosphate and glyceraldehyde-2-phosphate, and induced by mixed valence double layer metal hydroxide minerals. The reactions proceed from dilute aqueous reactant solutions (1.5 mM) at near neutral pH. Conditions have been established, where ribose-2,4-bisphosphate is the major product (approximately 48%) among the pentose-2,4-bisphosphates, which are formed with up to 25% yield.

Abiotic formation of hydrocarbons and oxygenated compounds during thermal decomposition of iron oxalate.

Abstract: The formation of organic compounds during the decomposition of iron oxalate dihydrate (IOD) was investigated as a possible analog for abiotic organic synthesis in geological systems. After heating at 330 degrees C for 2-4 days, IOD decomposed to a mixture of the minerals siderite and magnetite plus gas and non-volatile organic compounds. The organic products included an extremely large variety of compounds, making identification of individual reaction products difficult. However, the non-volatile products were dominated by several homologous series of alkylated cyclic compounds mostly containing a single aromatic ring, including alkylphenols, alkylbenzenes, alkyltetrahydronaphthols, and alkyltetrahydronaphthalenes. Traces of n-alkanols, n-alkanoic acids, n-alkanones, and n-alkanes were also identified. Carbon in the gas phase was predominantly CO2 (+CO?), with lesser amounts of light hydrocarbons to > C6 including all possible branched and normal isomers of the alkanes and alkenes. The organic products were apparently the result of two concurrent reaction processes: (1) condensation of the two-carbon units present in the initial oxalate moiety, and (2) Fischer-Tropsch-type synthesis from CO2 or CO generated during the experiment. Compounds produced by the former process may not be characteristic of synthesis from the single-carbon precursors which predominate in geologic systems, suggesting iron oxalate decomposition may not provide a particularly suitable analog for investigation of abiotic organic synthesis. When water was included in the reaction vessels, CO2 and traces of methane and light hydrocarbon gases were the only carbon products observed (other than siderite), suggesting that the presence of water allowed the system to proceed rapidly towards equilibrium and precluded the formation of metastable organic intermediates.

Prebiotic formation of adp and atp from amp, calcium phosphates and cyanate in aqueous solution

Abstract: Adenosine-5′-triphosphate was synthesized by the phosphorylation of adenosine-5′-diphosphate in aqueous solution containing cyanate as a condensing reagent and insoluble calcium phosphate produced from phosphate and calcium chloride. In a similar manner, adenosine-5′-diphosphate was synthesized from adenosine-5′-monophosphate. When the experiment was carried out in the conditions of 4 °C and pH 5.75, the formation of adenosine-5′-diphosphate and adenosine-5′-triphosphate from adenosine-5′-monophosphate was observed in the yields of 19 and 7%, respectively. The other nucleoside-5′-triphosphates were also produced from their respective diphosphates.

Nucleoside Phosphorylation: A Feasible Step in the Prebiotic Pathway to RNA

Abstract: Plausible prebiotic conditions for the phosphorylation of nucleosides by inorganic phosphate were reported by Lohrmann and Orgel in 1971. This reaction was carried out on heated dry films and promoted by urea. The major products formed were nucleoside-2:3 cyclicPs;5-NMPs and other derivatives were also formed. Minor modifications of the Lohrmann and Orgel system have resulted in the preferential formation of 5-NMPs. In this modified system a 2-fold preference for phosphorylation of the 5-OH group over the 3(2)-OH group was observed and the formation of other derivatives was minimized. The small amounts of bis compounds that were formed in this system could be quantitatively removed by selective binding to the mineral hydroxylapatite at moderate ionic strengths. It was also discovered that under hydrolytic conditions there was a 3:1 preference for removal of phosphates attached to the 3-OH group over the 5-OH group. A recycling procedure for obtaining additonal 5-NMPs from bis compounds and 3-NMPs is proposed.

Chirality amplification--the accumulation principle revisited.

Abstract: The chirality amplification mechanism proposed by Yamagata in 1966, relying on an Accumulation Principle which involved the parity violating energy difference (1 + e) presumed to be operative at each step in the formation of a homochiral biopolymer, is briefly surveyed historically. The Accumulation Principle is then examined analytically and found to be incapable of producing a unique homochiral polymer in any realistic polymerization process. The extension of the Accumulation Principle to crystallizations which afford enantiomorphic crystals is also scrutinized and found to be misapplied and invalid.

Survival of Life on Asteroids, Comets and Other Small Bodies

Abstract: The ability of living organisms to survive on the smaller bodies in our solar system is examined. The three most significant sterilizing effects include ionizing radiation, prolonged extreme vacuum, and relentless thermal inactivation. Each could be effectively lethal, and even more so in combination, if organisms at some time resided in the surfaces of airless small bodies located near or in the inner solar system. Deep within volatile-rich bodies, certain environments theoretically might provide protection of dormant organisms against these sterilizing factors. Sterility of surface materials to tens or hundreds of centimeters of depth appears inevitable, and to greater depths for bodies which have resided for long periods sunward of about 2 A.U.

Sources and sinks for ammonia and nitrite on the early Earth and the reaction of nitrite with ammonia.

Abstract: An analysis of sources and sinks for ammonia and nitrite on the early Earth was conducted. Rates of formation and destruction, and steady state concentrations of both species were determined by steady state kinetics. The importance of the reaction of nitrite with ammonia on the feasibility of ammonia formation from nitrite was evaluated. The analysis considered conditions such as temperature, ferrous iron concentration, and pH. For sinks we considered the reduction of nitrite to ammonia, reaction between nitrite and ammonia, photochemical destruction of both species, and destruction at hydrothermal vents. Under most environmental conditions, the primary sink for nitrite is reduction to ammonia. The reaction between ammonia and nitrite is not an important sink for either nitrite or ammonia. Destruction at hydrothermal vents is important at acidic pH's and at low ferrous iron concentrations. Photochemical destruction, even in a worst case scenario, is unimportant under many conditions except possibly under acidic, low iron concentration, or low temperature conditions. The primary sink for ammonia is photochemical destruction in the atmosphere. Under acidic conditions, more of the ammonia is tied up as ammonium (reducing its vapor pressure and keeping it in solution) and hydrothermal destruction becomes more important.

The extraterrestrial origin of the homochirality of biomolecules--rebuttal to a critique.

Abstract: Having concluded that abiotic terrestrial mechanisms would have been ineffectual for the origin of terrestrial homochirality, we have proposed an alternative extraterrestrial scenario involving stereoselective ultraviolet photolysis of the racemic constituents of interstellar grain mantles by circularly polarized synchrotron radiation from neutron stars, followed by terrestrial accretion of the resulting chiral molecules via cometary impact. Recently L. Keszthelyi (1995) has reviewed a number of our arguments and advanced several erroneous calculations and conclusions purporting to negate them. We offer here points of rebuttal to Keszthelyi's criticisms, and support our inferences with recent data regarding indigenous enantiomeric excesses of L-amino acids in the Murchison meteorite.

Mutual Amino Acid Catalysis in Salt-Induced Peptide Formation Supports this Mechanism's Role in Prebiotic Peptide Evolution

Abstract: The presence of some amino acids and dipeptides under the conditions of the salt-induced peptide formation reaction (aqueous solution at 85 °C, Cu(II) and NaCl) has been found to catalyze the formation of homopeptides of other amino acids, which are otherwise produced only in traces or not at all by this reaction. The condensation of Val, Leu and Lys to form their homodipeptides can occur to a considerable extent due to catalytic effects of other amino acids and related compounds, among which glycine, histidine, diglycine and diketopiperazine exhibit the most remarkable activity. These findings also lead to a modification of the table of amino acid sequences preferentially formed by the salt-induced peptide formation (SIPF) reaction, previously used for a comparison with the sequence preferences in membrane proteins of primitive organisms

Post-Viking microbiology: new approaches, new data, new insights.

Abstract: In the 20 years since the Viking experiments, major advances have been made in the areas of microbial systematics, microbial metabolism, microbial survival capacity, and the definition of environments on earth, suggesting that life is more versatile and tenacious than was previously appreciated. Almost all niches on earth which have available energy, and which are compatible with the chemistry of carbon-carbon bonds, are known to be inhabited by bacteria. The oldest known bacteria on earth apparently evolved soon after the formation of the planet, and are heat loving, hydrogen and/or sulfur metabolizing forms. Among the two microbial domains (kingdoms) is a great deal of metabolic diversity, with members of these forms being able to grow on almost any known energy source, organic or inorganic, and to utilize an impressive array of electron acceptors for anaerobic respiration. Both hydrothermal environments and the deep subsurface environments have been shown to support large populations of bacteria, growing on energy supplied by geothermal energy, thus isolating these ecosystems from the rest of the global biogeochemical cycles. This knowledge, coupled with new insights into the history of the solar system, allow one to speculate on possible evolution and survival of life forms on Mars.

Prebiotic synthesis of vitamin B6-type compounds.

Abstract: Heating a dilute solution of NH3 and glycoaldehyde gives a large family of pyridines substituted with the same functional groups as occur in the forms of vitamin B6. Thus, vitamin B6-like molecules could have been present on the early Earth and could have been available for catalysis of primitive transamination reactions. Ethanolamine and N-methylethanolamine are also formed as major products. These are choline-like molecules, the latter of which is apparently formed by a prebiotic methylation process.

Scanning tunnelling microscopy and molecular modelling of xanthine monolayers self-assembled at the solid-liquid interface: relevance to the origin of life.

Abstract: The development of scanning tunnelling microscopy (STM) has allowed examination of inorganic crystalline surfaces and their interactions with organic adsorbates with unparalleled resolution. As a novel technique in origin of life studies, the application of STM is detailed with particular attention paid to the methods employed in the analysis of organic monolayer structures. STM imaging and molecular modelling of self-assembled monolayers of the purine base, xanthine, formed on the surfaces of graphite and molybdenum disulfide are presented as an example. The putative role of such structures in the origin of life is discussed.

Pyrite suspended in artificial sea water catalyzes hydrolysis of adsorbed ATP: enhancing effect of acetate.

Abstract: Minerals have been implicated in different catalytic processes during chemical evolution It has been proposed that exergonic synthesis of pyrite (FeS2) could have served to promote the endergonic synthesis of biomonomers in early stages of life formation on Earth The present study was aimed to investigate whether pyrite can adsorb nucleotides and oxo acids in the potentially mild prebiotic conditions found away from the hot hydrothermal vents It is shown that pyrite strongly adsorbs adenosine 5′-triphosphate in an artificial medium that simulates primordial aqueous environments, and that adsorption is enhanced in the presence of acetate and in an oxygen-free atmosphere Moreover, the mineral catalyzes the sequential hydrolysis of the γ and β phosphoanhydride bonds of the nucleotide

Extraterrestrial Handedness: A Reply

Abstract: Recent investigations of stable isotope ratios of amino acids from the Murchison meteorite have shown them to be of unambiguous extraterrestrial origin, and examinations of their enantiomeric compositions, where terrestrial contamination can be excluded, have found a consistent excess of L-enantiomers. One explanation for this observation has been the asymmetric photolysis of racemic extraterrestrial amino acids by circularly polarized light (CPL) in the synchrotron radiation from orbiting electrons around the pulsar remnants of supernovae. Mason (1997) has attempted to discredit this mechanism on the grounds that circular dichroism (CD) bands for optically active molecules alternate in sign and sum to zero over the entire spectrum, and hence enantioselective photochemical reactions cannot be induced by broad band CPL. We submit arguments disputing this conclusion and present reasons for expecting that broad band CPL synchrotron radiation would be quite capable of inducing asymmetric photolysis, particularly in aliphatic amino acids.

Relative Reactivity of Ribosyl 2′-OH vs. 3′-OH in Concentrated Aqueous Solutions of Phosphoimidazolide Activated Nucleotides

Abstract: Phosphoimidazolide activated ribomononucleotides (*pN, see structure) are useful substrates for the non-enzymatic synthesis of oligonucleotides In the presence of metal ions, aqueous solutions of *pN yield primarily the two internucleotide-linked (pN2' pN and pN3' pN) and the pyrophosphate-linked (N5' ppN) dimers Small amounts of cyclic dimers and higher oligomers are also produced In this study the relative reactivity of 2'-OH vs 3'-OH was determined from the ratio of the yields of pN2' pN vs pN3' pN Experiments were performed at 23 degrees C in the range 72 < or = pH < or = 84 with substrates that differ in nucleobase (guanosine (G), cytidine (C), uridine (U), and adenosine (A)) and leaving group (imidazole (Im), 2-methylimidazole (2-MeIm) and 2,4-dimethylimidazole (2,4-diMeIm)) Two metal ions (Mg2+ or Mn2+) were employed as catalysts The conditions used here, ie a substrate concentration in the range 01 M to 10 M and metal ion concentration in the range 005 M to 02 M, favor base-stacking interactions The ratio pN2' pN: pN3' pN = 2'-5': 3'-5' was found independent of nucleobase and typically varied between 2 to 3 indicating that the 2'-OH is about 2 to 3 times more reactive than the 3'-OH *pN with Im, compared to 2-MeIm and 2,4-diMeIm leaving group, produce lower yields of internucleotide linked dimers, and a higher pN2' pN: pN3' pN ratio Trends in the data, observed with all three leaving groups, suggest an increase in pN2' pN: pN3' pN ratio with decreasing substrate concentration (up to 547 with 0051 M ImpG) The observations are in accord with earlier studies reporting a relative reactivity 2'-5': 3'-5' = 6 to 9 obtained with Im as the leaving group, in dilute nucleotide solutions and under conditions that disfavor stacking It is speculated that the concentration induced change in the relative reactivity is the result of self-association via base-stacking that enhances selectively the proximity of the 3'-OH of one molecule to the reactive P-N bond of an other molecule The implication of these conclusions for oligomerization/ligation reactions is discussed

Flash heating on the early Earth.

Abstract: It has been suggested that very large impact events (approximately 500 km diameter impactors) sterilized the surface of the young Earth by producing enough rock vapor to boil the oceans. Here, we consider surface heating due to smaller impactors, and demonstrate that surface temperatures conductive to organic synthesis resulted. In particular, we focus on the synthesis of thermal peptides. Previously, laboratory experiments have demonstrated that dry heating a mixture of amino acids containing excess Asp, Glu, or Lys to temperatures approximately 170 degrees C for approximately 2 hours yields polypeptides. It has been argued that such temperature conditions would not have been available on the early Earth. Here we demonstrate, by analogy with the K/T impact, that the requisite temperatures are achieved on sand surfaces during the atmospheric reentry of fine ejecta particles produced by impacts of bolides approximately 10-20 km in diameter, assuming approximately 1-100 PAL CO2. Impactors of this size struck the Earth with a frequency of approximately 1 per 10(4)-10(5) y at 4.2 Ga. Smaller bolides produced negligible global surface heating, whereas bolides > 30 km in diameter yielded solid surface temperatures > 1000 K, high enough to pyrolyze amino acids and other organic compounds. Thus, peptide formation would have occurred globally for a relatively narrow range of bolide sizes.