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Organic synthesis processes, which may have occurred in the primitive earth atmosphere or in comets, produced in the laboratory by methods of electric discharge, uv light and ionizing radiation

The LnBaCo2O5+δ cobaltites with ordered A-site cations exhibit a very rich phase diagram as a function of the oxygen content, which determines the doping of CoO2 planes. By means of thermogravimetry analysis (TGA), we study the appropriate way to tailor oxygen contents in PrBaCo2O5+δ compounds. Starting from an air-synthesized sample, we study the evolution of δ during different heat treatments with “in situ” TGA measurements. We find that δ can be tailored from δ ≃ 0.2 to δ ≃ 0.9. Thermogravimetry measurements also show that oxygen ions can flow through (0 0 1) PrOδ planes at relatively low temperatures (200 °C, this temperature increases in compounds with smaller rare earths). By means of neutron powder diffraction at room temperature, we determine the structural details and study the eventual order of oxygen vacancies for different values of δ.

Electrochemical oxidation at room temperature of a slurry of Ag2Cu2O3 yields a new silver copper oxide, formulated as Ag2Cu2O4, with one more atom of oxygen per unit formula, that can in turn revert to the original precursor. The resulting oxide presents a different electronic and crystal structure from its precursor, as shown by XPS, X-ray and electron diffraction. This phase transformation involves a radical structural change from a 3D to a 2D network, as well as electronic changes involving silver and oxygen. The potential of electrochemical techniques to induce crystal-chemical solid state transformations is analyzed., The authors thank J.P. Espinós, Fundación Domingo Martínez and the MCYT grants (PB98-0491 and MAT2002-04529-C03).

In this work we consider the role of phosphorus in chemical evolution from an interdisciplinary approach. First we briefly review the presence of this element in different cosmic sites, such as massive stellar cores, circumstellar and interstellar clouds, meteorites, lunar and Martian samples, interplanetary dust particles, cometary dust and planetary atmospheres. Thus we illustrate the fact that phosphorus seems to be, at the same time, scarce and ubiquitous in the solar system. Afterwards, by comparing the phosphorus content of our planet's main reservoirs with the amount of cometary and meteoritic matter captured by the primitive Earth, we conclude that comets may have provided a primary source for phosphorus compounds of prebiotic interest. Finally, we make a number of proposals aimed to gain observational supporting evidence to the above conclusion and other suggestions made in the article.

The hypothesis that vestiges of the ancestral RNA-dependent RNA polymerase involved in the replication of RNA genomes of Archean cells are present in the eubacterial RNA-polymerase beta-prime subunit and its homologues is discussed. It is shown that, in the DNA-dependent RNA polymerases from three cellular lineages, a very conserved sequence of eight amino acids, also found in a small RNA-binding site previously described for the E. coli polynucleotide phosphorylase and the S1 ribosomal protein, is present. The optimal conditions for the replicase activity of the avian-myeloblastosis-virus reverse transcriptase are presented. The evolutionary significance of the in vitro modifications of substrate and template specificities of RNA polymerases and reverse transcriptases is discussed.

The prebiotic synthesis of His and its dimer has led us to study the possible catalytic properties of His-His. The enhancing effect of His-His has been tested in the dephosphorylation of dAMP, the hydrolysis of oligo(A)12, and the oligomerization of 2'3'-cAMP.

The prebiotic formation of histidine (His) has been accomplished experimentally by the reaction of erythrose with formamidine followed by a Strecker synthesis. In the first step of this reaction sequence, the formation of imidazole-4-acetaldehyde took place by the condensation of erythrose and formamidine, two compounds that are known to be formed under prebiotic conditions. In a second step, the imidazole-4-acetaldehyde was converted to His, without isolation of the reaction products by adding HCN and ammonia to the reaction mixture. LC, HPLC, thermospray liquid chromatography-mass spectrometry, and tandem mass spectrometry were used to identify the product, which was obtained in a yield of 3.5% based on the ratio of His/erythrose. This is a new chemical synthesis of one of the basic amino acids which had not been synthesized prebiotically until now.

In order to prepare poly(N-vinyl carbazole) (PVK) and carbon nanotube (CNs) based composites, electrochemical polymerization of N-vinyl carbazole (NVK) was studied by cyclic voltammetry (CV) in LiClO4/acetonitrile solutions. Cyclic voltammograms recorded on a blank Pt electrode and those obtained when single or multi-walled carbon nanotubes (SWNTs or MWNTs) films were previously deposited onto the Pt electrode show a down-shift of the VK reduction peak potential in the latter case. The influence of monomer concentration and supporting electrolyte on the polymerization conditions and electrochemical properties of these composite materials were also investigated. Morphologic aspects as well as the photoluminescence properties of the PVK/CNs composite were also investigated. A covalent functionalization of carbon nanotubes with PVK is suggested on the basis of infrared (IR) spectroscopic studies. Using the PVK/CN composite as a positive electrode and an electrolytic solution containing LiPF6, a higher specific discharge capacity of the rechargeable lithium cells, 45 and 115 mA h g−1, are reported for PVK functionalized SWNTs and MWNTs, respectively., A post-doctoral fellowship to M.B. by the Spanish Ministry of Science is gratefully acknowledged. Partial funding from the Spanish Ministry of Science and Technology (Grant No. MAT 2002-04529-C03) is also acknowledged.

The structure of Ag2Cu2O4 synthesized by electrochemical oxidation of its precursor Ag2Cu2O3 is studied under a new perspective. Irradiation of the oxide with X-ray beam transforms the electronic structure of the phase by redistributing the internal charge within the material. The refined structure shows several possibilities all with metals in the same arrangement, but with oxygen atoms distributed in a rather disordered way. This is typical of ionic conductors., The authors want to thank the Fundación Domingo Martínez for a grant and the Ministry of Science for a fellowship for D.M. Rojas and for grants PB98-0491 and MAT98-0807-C02-02.

The most frequently invoked explanation for the origin of metabolic pathways is the retrograde evolution hypothesis. In contrast, according to the so-called "patchwork" theory, metabolism evolved by the recruitment of relatively inefficient small enzymes of broad specificity that could react with a wide range of chemically related substrates. In this paper it is argued that both sequence comparisons and experimental results on enzyme substrate specificity support the patchwork assembly theory. The available evidence supports previous suggestions that gene duplication events followed by a gradual neoDarwinian accumulation of mutations and other minute genetic changes lead to the narrowing and modification of enzyme function in at least some primordial metabolic pathways.

Reverse transcriptase (RT) was first discovered as an essential catalyst in the biological cycle of retroviruses. However, in the past years evidence has accumulated showing that RTs are involved in a surprisingly large number of RNA-mediated transpositional events that include both viral and nonviral genetic entities. Although it is probable that some RT-bearing genetic elements like the different types of AIDS viruses and the mammalian LINE family have arisen in recent geological times, the possibility that reverse transcription first took place in the early Archean is supported by (1) the hypothesis that RNA preceded DNA as cellular genetic material; (2) the existence of homologous regions of the subunit tau of the E. coli DNA polymerase III with the simian immunodeficiency virus RT, the hepatitis B virus RT, and the beta' subunit of the E. coli RNA polymerase (McHenry et al. 1988); (3) the presence of several conserved motifs, including a 14-amino-acid segment that consists of an Asp-Asp pair flanked by hydrophobic amino acids, which are found in all RTs and in most cellular and viral RNA polymerases. However, whether extant RTs descend from the primitive polymerase involved in the RNA-to-DNA transition remains unproven. Substrate specificity of the AMV and HIV-1 RTs can be modified in the presence of Mn2+, a cation which allows them to add ribonucleotides to an oligo (dG) primer in a template-dependent reaction. This change in specificity is comparable to that observed under similar conditions in other nucleic acid polymerases. This experimentally induced change in RT substrate specificity may explain previous observations on the misincorporation of ribonucleotides by the Maloney murine sarcoma virus RT in the minus and plus DNA of this retrovirus (Chen and Temin 1980). Our results also suggest that HIV-infected macrophages and T-cell cells may contain mixed polynucleotides containing both ribo- and deoxyribonucleotides. The evolutionary significance of these changes in substrate specificities of nucleic acid polymerases is also discussed.

Different estimates based on dynamical considerations, lunar cratering rates, Solar System chemical abundances, and the single-impact theory on the origin of the Earth-Moon system suggest that comets and other related small, volatile-rich primitive minor bodies captured by the Earth during the early Archean must have been a major source of volatiles on our planet. It is likely that a substantial fraction of the organic molecules present in the colliding cometary nuclei, which may have included nitrogen bases and the precursors of amino acids, were destroyed due to the high temperatures and shock wave energy associated with the collision. However, the presence of H2O, CN, CH, CO, CO2 and other carbon-bearing molecules and radicals in the atmosphere of the Sun and in circumstellar shells around carbon-rich stars suggests that at least simple carbon species could have survived the cometary collisions. Under the anoxic conditions thought to prevail in the prebiotic terrestrial paleoatmosphere, the post-collisional formation of a large number of excited molecules and radicals, and the rapid quenching of the expanding gaseous ball may have led, upon rapid cooling, to the formation of molecules of biogenic elements and to their eventual deposition in localized environments where complex organic compounds of biochemical significance may have been produced and accumulated.

The nonenzymatic synthesis of the coenzymes adenosine diphosphate glucose (ADPG), guanosine diphosphate glucose (GDPG), and cytidine diphosphoethanolamine (CDP-ethanolamine) has been carried out under conditions considered to have been prevalent on the early Earth. The production of these compounds was performed by allowing simple precursor molecules to react under aqueous solutions, at moderate temperatures and short periods of time, with mediation by cyanamide or urea. These two condensing agents are considered to have been present in significant amounts on the primitive Earth and have been previously used in the nonenzymatic synthesis of several other important biochemical compounds. In our experiments, ADPG was obtained by heating glucose-1-phosphate (G1P) and ATP in the presence of cyanamide for 24 h at 70 degrees C. The reaction of G1P and GTP under the same conditions yielded GDPG. The cyanamide-mediated production of CDP-ethanolamine was carried out by reacting a mixture of ethanolamine phosphate and CTP for 24 h at 70 degrees C. The separation and identification of the reaction products was carried out by paper chromatography, thin-layer chromatography, high performance thin-layer chromatography, high performance liquid chromatography, both normal and reverse-phase, UV spectroscopy, enzymatic assays, and acid hydrolysis. Due to the mild conditions employed, and to the relative ease of these reactions, these studies offer a simple attractive system for the nonenzymatic synthesis of phosphorylated high-energy metabolic intermediates under conditions considered to have been prevalent on the ancient Earth.

The synthesis of putrescine was accomplished by decarboxylation of L-ornithine when this amino acid was heated in aqueous solution and in the absence of oxygen. Chromatographic, radioisotopic, and enzymatic techniques were used to demonstrate that one mole of non-radioactive putrescine and one mole of 14CO2 was formed during the heating of L-(l-14C)-ornithine. This work indicates that the synthesis of putrescine can occur starting with ornithine and in conditions that are presumed could have existed on the primitive Earth. The possible significance of these results in the prebiotic molecular evolution is briefly discussed.

Some properties of DNA condensed with spermidine have been compared with the properties of DNA condensed with Co3+(NH3)6 to determine whether condensation of DNA with these trivalent cations protects DNA against the action of DNase I and increases transcription and encapsulation of DNA into liposomes. It was shown that DNA condensed with Co3+(NH3)6 was resistant to the action of the endonuclease DNase I such as DNA condensed with spermidine was. However, DNA condensed with Co3+(NH3)6 was significantly less active in transcription with the E. coli RNA polymerase than DNA-spermidine condensed forms. In addition, it was demonstrated that both compacted forms of DNA were more efficiently encapsulated into neutral liposomes; however, negatively, charged liposomes were scarcely formed in the presence of DNA condensed with Co3+(NH3)6. These experiments and the well documented properties of polyamines increasing the resistance to radiations and hydrolysis of nucleic acids, as well as their biological activities, such as replication, transcription, and translation, together with the low concentration of Co3+ in the environment, lead us to propose spermidine as a plausible prebiotic DNA condensing agent rather than Co3+ and the basic proteins proposed by other authors. Then, we consider the possible role and relevance of the polyamine-nucleic acids complexes in the evolution of life.

Transbilayer diffusion of Mn2+ ions occurred in liposomes formed from dipalmitoyl-phosphatidylcholine or egg-yolk phosphatidylcholine and egg-yolk phosphatidate (molar ratio 2∶1) containing DNA and DNase I within their aqueous compartments. Cation diffusion was demonstrated by the hydrolytic activity of DNase I, activated by the Mn2+ ions that diffused into the vesicles, and this was confirmed by light scattering. Phosphatidate, a cone-shaped lipid which has been synthesized under simulated prebiotic conditions, was necessary for cation diffusion across the liposome membranes. Such liposomes represent a simple precellular system that interchanges cations with the surroundings and provides a microenvironment for enzymatic reactions, as evidenced by the hydrolysis of DNA by DNase I inside these closed lipid compartments.

Histidyl-histidine (His-His) has been synthesized in a yield of up to 14.4% under plausible prebiotic conditions using histidine (His), cyanamide, and 4-amino-5-imidazole carboxamide. A trace amount of His trimer was also detected. Because the imidazole group of His is involved in a number of important enzymatic reactions, and His-His has been shown to catalyze the prebiotic synthesis of glycyl-glycine, we expect this work will stimulate further studies on the catalytic activities of simple His-containing peptides in prebiotic reactions.

According to Oparin, Mendeleev thought that the origin of petroleum was the result of the hydrolysis of iron carbides by superheated steam under pressure from the deep interior of the Earth through geological formations where the metal carbides exist. As early as 1877, Mendeleev described the reaction leading to the synthesis of hydrocarbons according to the general equation 3Fe(sub m)C(sub n) + mH2O yields mFe3O4 + C(sub 3n)H(sub 8m). Other experimental studies on the production of hydrocarbons from cast iron have been reported. Because of the possibility that hydrocarbons may have been trapped within the carbon matrix of the cast iron, which usually has a high content of carbon, we have studied the reaction of pure iron carbide with deuterium chloride and deuterated water. This was done in order to distinguish any newly formed deuterated hydrocarbons from any possible impurities of trapped hydrocarbons. The experiments were carried out by simply allowing iron carbide to react with concentrated deuterium chloride in D2O. The volatile hydrocarbon fraction examined by gas chromatography-mass spectrometry (GC/MS), using a Finnigan 1020/OWA instrument. contained low molecular weight hydrocarbons in a range C3 to C7. Lower molecular weight hydrocarbons were not detected by GC/MS because the MS scanning mode was preset above mass 40 to exclude components of air. The identified hydrocarbons are similar to those obtained under prebiotic conditions using high frequency discharge. The hydrocarbons found in common were propane, butane, pentane, 3-methylpentane, hexane, and heptane. The percent yields decline with increasing carbon number (propane 11%, n-heptane 1%). Similar results have been obtained by the direct treatment of metal carbides by pulse laser vaporization mass spectrometry. These results show that the hydrolysis of iron carbides may have been a significant source of hydrocarbons on the primitive Earth. There appears to be a predominance of straight chain isomers, which may have been important in the prebiotic synthesis of membrane-forming compounds.

The synthesis of palmitoylglycerols in good yields occurs when a solution of glycerol, ammonium palmitate, cyanamide and imidazole is dried and heated at ambient humidity at temperatures ranging from 60 degrees--100 degrees C for 16 h. Much less product is formed in the absence of either or both cyanamide or imidazole. This work suggests that acylglycerols could have been synthesized on the primitive Earth under plausible prebiotic conditions which were similar but not identical to those which have been shown to condense deoxynucleotides into oligodeoxynucleotides and amino acids into peptides.

When an aqueous solution (pH 7.0) of 3H deoxythymidine 5'-triphosphate, deoxythymidine 5'-phosphate, 4-amino-5-imidazolecarboxamide, cyanamide and ammonium chloride was dried and heated at 60 degrees C for 18 h, oligomers were obtained in a yield of approximately 80%. After the chemical degradation of any pyrophosphate bonds present in these oligomers, linear polynucleotides of up to 7-8 units in length were isolated by DEAE cellulose column chromatography and identified by enzymatic digestion procedures. The di- and trinucleotide fractions were degraded 87% and 100% by snake venom phosphodiesterase and 39% and 9% by spleen phosphodiesterase. This synthesis of deoxythymidine oligonucleotides was conducted under potentially prebiotic conditions and may offer a possible method for the synthesis of deoxyoligonucleotides on the primitive Earth.

More than thirty polycyclic aromatic hydrocarbons, including nine heterocyclic aromatic compounds, have been identified in solvent extracts of the Murchison meteorite by gas chromatography-mass spectrometry using bonded-phase fused silica columns. Structural isomers of several alkylated aromatic hydrocarbons, including methylpyrene and methylphenanthrene were chromatographically separated, thus allowing calculations of the amount of alkyl substituted compounds in the solvent extracts. The ratio of odd-carbon number to even-carbon number was found to be approximately 0.1. Based on these data and literature data from model pyrolysis experiments, a temperature of 1000°C is suggested for the formation of polycyclic aromatic hydrocarbons in the solar nebula or premeteoritic body. The value of 1000°C is within the range of temperatures for the condensation of the nebular material from the initial high temperature phases to the lower temperature phases at which chemical and isotopic equilibria were frozen. A simple model for the abiotic synthesis of heterocyclic compounds from simple aliphatic precursors is also presented.

Experiments were performed in which meteoritic iron, iron ore and nickel-iron alloy were used to catalyze (in Fischer-Tropsch synthesis) the reaction of deuterium and carbon monoxide in a closed vessel. Normal alkanes and alkenes and their monomethyl substituted isomers and aromatic hydrocarbons were synthesized. Iron oxide and oxidized-reduced Canyon Diablo used as Fischer-Tropsch catalysts were found to produce aromatic hydrocarbons in distributions having many of the features of those observed in carbonaceous chondrites, but only at temperatures and reaction times well above 300 C and 6-8 h.

The neutral lipids of nine methanogenic and three thermoacidophilic bacteria were analyzed. The major compounds are acyclic isoprenoids in the range of C15 to C30. The compounds were identified by means of their mass spectral fragmentation pattern and/or by co-chromatography. A high similarity is seen between the isoprenoid content of the examined bacteria and the distribution of these compounds in ancient sediments and petroleum.

The synthesis of purines and pyrimidines using Oparin-Urey-type primitive Earth atmospheres has been demonstrated by reacting methane, ethane, and ammonia in electrical discharges. Adenine, guanine, 4-aminoimidazole-5-carboxamide (AICA), and isocytosine have been identified by UV spectrometry and paper chromatography as the products of the reaction. The total yields of the identified heterocyclic compounds are 0.0023%. It is concluded that adenine synthesis occurs at a much lower concentration of hydrogen cyanide than has been shown by earlier studies. Pathways for the synthesis of purines from hydrogen cyanide are discussed, and a comparison of the heterocyclic compounds that have been identified in meteorites and in prebiotic reactions is presented.

During the last three decades major advances have been made in our understanding of the formation of carbon compounds in the universe and of the occurence of processes of chemical evolution. 1) Carbon and other biogenic elements (C,H,N,O,S and P) are some of the most abundant in the universe. 2) The interstellar medium has been found to contain a diversity of molecules of these elements. 3) Some of these molecules have also been found in comets which are considered the most primordial bodies of the solar system. 4) The atmospheres of the outer planets and their satellites, for example, Titan, are actively involved in the formation of organic compounds which are the precursors of biochemical molecules. 5) Some of these biochemical molecules, such as amino acids, purines and pyrimidines, have been found in carbonaceous chondrites. 6) Laboratory experiments have shown that most of the monomers and oligomers necessary for life can be synthesized under hypothesized but plausible primitive Earth conditions from compounds found in the above cosmic bodies. 7) It appears that the primitive Earth had the necessary and sufficient conditions to allow the chemical synthesis of biomacromolecules and to permit the processes required for the emergence of life on our planet. 8) It is unlikely that the emergence of life occurred in any other body of the solar system, although the examination of the Jovian satellite Europa may provide important clues about the constraints of this evolutionary process. Some of the fundamental principles of chemical evolution are briefly discussed.

One of the major diagenetic pathways of organic matter in recent sediments involves the condensation of cellular constituents, particularly amino acids and sugars, into insoluble melanoidin-type polymers. These polymers consist mainly of humic and fulvic acids and make up the major part of the organic carbon reservoir in recent sediments. We suggest that a similar set of reactions between abiotically formed amino acids and sugars, and more generally between aldehydes and amines, occurred on a large scale in the prebiotic hydrosphere. The rapid formation of this insoluble polymeric material would have removed the bulk of the dissolved organic carbon from the primitive oceans and would thus have prevented the formation of an "organic soup". Melanoidin polymers have several properties which make them attractive hypothetical precursors of contemporary oxidation-reduction coenzymes: 1. they contain heterocyclic nitrogen compounds similar to the nitrogenous bases; 2. they contain a high concentration of stable free radicals; and 3. they tend to concentrate those heavy metals which play prominent roles in contemporary enzymic redox processes. The prebiotic formation of similar polymers could, therefore, have provided the starting point for a basic class of biochemical reactions. We suggest that the prebiotic scenario involved chemical and protoenzymic reactions at the sediment-ocean interface in relatively shallow waters and under conditions not much different from those of the recent environment.

Commercial microbiological processes frequently contain dispersed microorganisms which are heterogeneous in their age, size, and composition. Relative protein and nucleic acid contents of individual bacteria in Bacillus subtilis submerged cultures have been measured experimentally using laser flow microfluorometry. Marginal and joint population composition density data and their complex patterns of evolution during batch growth provide an impetus and emerging basis for a new generation of potentially robust mathematical models of microbial systems.

In this review an attempt is made to highlight the structures and properties of clay that may contribute to a better understanding of the role of clays in chemical evolution. The adsorption of organic molecules on clays has been demonstrated, as has the synthesis of bioorganic monomers in the presence of clays. For instance, amino acids (glycine, aspartic acid, threonine, alanine and others) as well as purines and pyrimidines, have been obtained from CO and NH3 in the presence of clays at relatively high temperatures (250-325 degrees C). Carbohydrates are also easily derived from formaldehyde at relatively low temperatures (approximately equal to 80 degrees C). The oligomerization of biochemical monomers, mediated by clays has also been shown to result in the formation of polymer molecules basic to life. For instance the condensation of amino acyl adenylates at room temperature in the presence of montmorillonite is known to yield polypeptides in discrete ranges of molecular weights with degrees of polymerization up to 56. Clays have also been found to affect the condensation of mononucleotides to oligonucleotides. Although the role of clays in the origin or metabolic pathways has not been demonstrated, it is possible that clays may have played a cooperative role with catalytic peptides in an intermediate stage of prebiological chemistry preceding the emergence of life on this planet.

Two studies on the abiotic formation of amino acids are presented. The first study demonstrates the role of hydrogen cyanide as a precursor of amino acids detected in extracts of lunar samples. The formation of several amino acids, including glycine, alanine, aspartic acid, and glutamic acid, under conditions similar to those used for the analysis of lunar samples is demonstrated. The second study investigates the formation of hydrogen cyanide as well as amino acids from lunar-sample gas mixtures under electrical discharge conditions. These results extend the possibility of synthesis of amino acids to planetary bodies with primordial atmospheres less reducing than a mixture of methane, ammonia, hydrogen and water.

The cell size and DNA and protein content of bacteroids fractionated from alfalfa and soybean nodules by buoyant density sedimentation were examined by laser flow-microfluorometry. In alfalfa nodules, these parameters were inversely related to bacteroid density. The bacteroids which sedimented at the highest density ( p = 1.268 ) resembled free-living Rhizobium meliloti in cell size and protein content but averaged slightly higher in DNA content. The bacteroids which sedimented at the lowest density ( p = 1.224 ) averaged larger in size and contained significantly more DNA and protein then free-living R. meliloti. Despite the difference in density, bacteroid fractions from soybean nodules and free-living Rhizobium japonicum were similar in all measured parameters.

An alkane distribution in which isoprenoid alkanes are present in excess of n -paraffins and pristane, phytane, and norpristane (in this order) are the major components, has been found in two different beds of the Irati oil shale, Brazilian Permian formation of Sao Mateus do Sul, Parana.

Using the model of a primitive earth evaporation pond, the synthesis of three histidyl peptides in yields up to 11% was demonstrated when aqueous solutions of histidine, leucine, ATP, cyanamide, and MgCl2 were evaporated and heated for 24 h at 80 degrees C. In addition, peptides were formed in yields of up to 56%, 35%, and 21%, respectively for phenylalanine, leucine, and alanine when aqueous solutions of the appropriate amino acid were evaporated and heated with cyanamide and one or more of the following components: ATP, AMP, 4-amino-5-imidazole carboxamide, or MgCl2. The greatest peptide yield occurred at pH 3. But peptide formation was demonstrated for a system of Leu, cyanamide, and MgCl2 adjusted to pH 7 with NH4OH. Peptide synthesis was also studied in the presence of CaCl2, ZnCl2, different adenosine nucleotides, and UTP to compare their effects on peptide synthesis. The optimum conditions for cyanamide mediated peptide synthesis were also studied in terms of pH, reaction time, reaction temperature, and cyanamide concentration. The major side product in nearly all reactions studied appears to be an amino acid-cyanamide adduct. Peptides were analyzed and identified by thin layer chromatography, acid hydrolysis, and enzymatic degradation.

The synthesis of uridine diphosphate glucose (UDPG), cytidine diphosphate choline (CDP-choline), glucose-1-phosphate (G1P) and glucose-6-phosphate (G6P) has been accomplished under simulated prebiotic conditions using urea and cyanamide, two condensing agents considered to have been present on the primitive Earth. The synthesis of UDPG was carried out by reacting G1P and UTP at 70 degrees C for 24 hours in the presence of the condensing agents in an aqueous medium. CDP-choline was obtained under the same conditions by reacting choline phosphate and CTP X G1P and G6P were synthesized from glucose and inorganic phosphate at 70 degrees C for 16 hours. Separation and identification of the reaction products have been performed by paper chromatography, thin layer chromatography, enzymatic analysis and ion pair reverse phase high performance liquid chromatography. These results suggest that metabolic intermediates could have been synthesized on the primitive Earth from simple precursors by means of prebiotic condensing agents.

The role and relative contributions of different forms of energy to the synthesis of amino acids and other organic compounds on the primitive earth, in the parent bodies or carbonaceous chondrites, and in the solar nebula are examined. A single source of energy or a single process would not account for all the organic compounds synthesized in the solar system. Electric discharges appear to produce amino acids more efficiently than other sources of energy and the composition of the synthesized amino acids is qualitatively and quantitatively similar to those found in the Murchison meteorite. Ultraviolet light is also likely to have played a major role in prebiotic synthesis. Although the energy in the sun's spectrum that can be absorbed by the major constituents of the primitive atmosphere is not large, reactive trace components such as H2S and formaldehyde absorb at longer wavelengths where greater amounts of energy are available and produce amino acids by reactions involving hot hydrogen atoms. The thermal reaction of CO + H2 + NH3 on Fischer-Tropsch catalysts generates intermediates that lead to amino acids and other organic compounds that have been found in meteorites. However, this synthesis appears to be less efficient than electric discharges and to require a special set of reaction conditions. It should be emphasized that after the reactive organic intermediates are generated by the above processes, the subsequent reactions which produce the more complet biochemical compounds are low temperature homogenous reactions occurring in an aqueous environment.

The only successful syntheses so far reported for the prebiotic formation of oligodeoxyribonucleotides involve the condensation, under warm aqueous conditions of deoxythymidine 5’-phosphate, using either cyanamide (Ibanez et al., 1971a, b) or imidazole (Ibanez et al., 1971b, c) as catalysts. In both condensations, oligomers of up to five units in length were obtained, but the total yields were less than 2%. The majority of syntheses which have led to the formation of oligoribonucleotides have been conducted under drying conditions at relatively high or moderate temperatures, the latter simulating the effects resulting from the drying up of primeval lakes and ocean beds (Moravek et al., 1968a, b, c; Tapiero and Nagyvary, 1971; Osterberg et al., 1973). In view of the success of these reactions it was decided to continue our work on the synthesis of oligodeoxyribonucleotides and to study the effects of drying conditions on the formation of these compounds.

The applicability of flow microfluorometry (FMF) to the study of chlorophyll-containing cells was investigated through the use of the blue-green alga Agmenellum quadruplicatum, the green algae Trebouxia, Chlorella, and Euglena spp., and isolated spinach chloroplasts. When excited by laser radiation (488 nm), algal cells emitted fluorescence with intensity positively related to the chloro phyll content. The chlorophyll fluorescent signals were used further as a differential criterion in determining relative size based on light scattering logic and to sort mixtures of algal cells having different chlorophyll content. The FMF also was useful in estimating nucleic acid and protein content in completely dechlorophyllized algal cells with the use of ethidium bromide (EB) and fluorescein isothiocyanate (FITC), respectively.

Deoxynucleoside 5'-monophosphates were condensed by cyanamide or by l-ethyl-3-(3-dimethylaminopropyl) carbodiimide in the presence of ammonium chloride at 0 degree, 37 degrees or 60 degrees C through several cycles of evaporation to dryness with replenishment of all reactants at each cycle. We found that at 37 degrees or 60 degrees cyanamide gives distinctly more high molecular weight material than does carbodiimide. Indeed, the yield of condensed products for the cyanamide reaction (dimers and higher oligomers) was found to be between 60 percent and 80 percent. The molecular weight distribution of the product shifts to higher molecular weights as cycling continues at 37 degrees or 60 degrees for both condensing agents. The water soluble carbodiimide gives higher yields of low molecular weight product but much lower yields of the higher molecular weight products. At 0 degree yields of high molecular weight product were low for both condensing agents. Results of characterization of the products demonstrate the synthesis of oligodeoxynucleotides including tetramers, with 3'-5' phosphodiester linkages.

The Precambrian is the longest and least understood period in the history of our planet. There is no direct evidence which bears on the primitive Earth environment, the synthesis of organic compounds and the origin of life on our planet, since the geological record only goes back to 3.8 Ga ago. To overcome this deficiency it is necessary to extrapolate backwards from 3.8 Ga ago to the time when the Earth was formed, ∼ 4.6 Ga ago, and also make use of additional scientific approaches. These include models of the solar nebula and planet formation, comparative observations with other cosmic environments, and experimental simulation studies under plausible primitive Earth conditions, particularly in regard to the prebiological synthesis of organic compounds. A large number of interstellar organic molecules have been detected by radioastronomy in the interstellar medium, particularly in places where other solar systems may be in the process of formation. It is remarkable that ∼ 10 of these molecules are known to be the precursors of the most important biochemical monomers. Furthermore, some of these monomers, e.g., amino acids, purines and pyrimidines, have also been detected in carbonaceous chondrites, which were presumably synthesized on the parent bodies of the meteorites or possibly in the solar nebula. Comparative studies on the terrestrial planets indicate that their primitive atmospheres resulted primarily from outgassing of CO2 and other partially oxidized (CO, N2) and reduced (H2, CH4, NH3, H2S) volatiles. Furthermore, comets and meteorites are thought to have made a significant contribution to the reduced carbon precursors for the prebiological synthesis of biochemical compounds. A brief review of the experiments carried out in the laboratory under possible primitive Earth conditions shows that amino acids, purines, pyrimidines, monosaccharides, fatty acids and other compounds are readily obtained using different energy sources. However, the formation of oligopeptides, oligonucleotides and phospholipids requires more restrictive conditions. They have been synthesized by means of condensing agents, such as cyanamide, as well as by heating under relatively dry conditions of less than 100°C. Experiments have been carried out on the formation of liposomes from prebiotically synthesized phospholipids. Also, using 2-methylimidazolide derivatives of nucleotides, the template directed synthesis of polynucleotides has been demonstrated. In the latter experiments a high fidelity of complementary base pairing has been observed, which if further improved would approach that of enzyme catalyzed replication. However, it is not known how the prebiologically synthesized polymers became organized into a self-replicating system. At any rate the first living systems were probably very rudimentary heterotrophic micro-organisms which used organic compounds from the environment for both cell components and energy. They were probably followed by fermenters and eventually by autotrophic CO2 reducing micro-organisms similar to the methanogenic and photosynthetic bacteria.

Peptides were formed in yields of 5%, 17% and 66%, respectively, when aqueous solutions of glycine, isoleucine or phenylalanine were dried and heated for 24 h at 90 degrees C with adenosine 5'-triphosphate, 4-amino-5-imidazolecarboxamide and cyanamide. Glycine and L-phenylalanine produced mixtures of di-, tri- and tetrapeptides, while L-isoleucine gave only the dipeptide in detectable quantities. The dipeptides of L-isoleucine and L-phenylalanine were identified by mass spectrometry and enzymatic and enzymatic degradation.

The influence of ammonia on the pyrolysis pattern of selected organic substances sorbed on an inorganic phase was investigated. The thermal degradation products were identified by gas chromatography-mass spectrometry. The feasibility of this technique was tested on a meteoritic sample. All substances examined react with ammonia at the pyrolysis temperature of 500 C, the major products being nitriles and heterocyclic compounds in which nitrogen was incorporated. Based on these results, a model for the non-equilibrium production of organic compounds on Jupiter is discussed. The investigation was performed in connection with the Viking lander molecular analysis. The results obtained indicate that the concentrations of ammonia in the retrorocket fuel exhaust would have been probably too small to produce significant changes in the Martian soil organic compounds if any were found.

The lipids of a thermophilic chemolithotroph,Metbanobacterium thermoautotropbicum, have been analyzed by chromatographic techniques and identified by infrared spectrometry and combined gas chromatography-mass spectrometry. Of the total chloroform soluble lipids 79% and 21% are polar and non-polar lipids, respectively. The major components of the polar lipids are dialkyl ethers of glycerol or its derivatives. The nature of the glycerol ether alkyl groups was found to be that of the saturated tetraisoprenoid hydrocarbon phytane. The non-polar lipids of the chloroform soluble fraction consist principally of three series of C20, C25 and C30 acyclic isoprenoid hydrocarbons, the major components being squalene and a continuous range of hydrosqualene derivatives, from dihydrosqualene up to and including decahydrosqualene. These data establish thatM. tbermoautotropbicum contains predominantly non-sapo-nifiable lipids as doHalobacterium, Halococcus, Sulfolobus andTbermoplasma. In particular, the composition of the chloroform soluble lipids ofM. tbermoautotropbicum is quite similar to that ofHalobacterium cutirubrum. The results strongly support the recent proposal, based on 16S rRNA sequence homologies, that the extreme halophiles and methanogens share a common ancestor. In addition, it is pointed out that the occurrence of phytane and related polyisoprenoid compounds in ancient sediments can no longer be considered unequivocally as indicative of past photosynthetic activity. Finally, speculations are made concerning the possible role of and evolutionary significance of the presence of squalene and hydrosqualenes in these organisms. To our knowledge this is the first report of squalene and hydrosqualenes in a strictly anaerobic microorganism.

The suggestion by Hoyle and Wickramasinghe (1978) that life might have originated in cometary nuclei rather than directly on the earth is discussed. Factors in the cometary environment including the conditions at perihelion passage leading to the ablation of cometary ices, ice temperatures, the absence of an atmosphere and discrete liquid and solid surfaces, weak cometary structure incapable of supporting a liquid core, and radiation are presented as arguments against biopoesis in comets. It is concluded that although the contribution of cometary and meteoritic matter was significant in shaping the earth environment, the view that life on earth originally arose in comets is untenable, and the proposition that the process of interplanetary infection still occurs is unlikely in view of the high specificity of host-parasite relationships.

A comparative study of the stable carbon isotopes, the aliphatic and aromatic hydrocarbons and the normal fatty acids in four differentiated organic phases (designated in this report as bitumens A, B, C and D) from Windy Knoll, Derbyshire, England, shows the following: 1. (1) The average abundances of 13C (relative to the P.D.B. standard and in parts per thousand) in the bitumens vary from −28.0 (bitumen B) to −30.7 (bitumen C) well within the range of petroleum. 2. (2) Isoprenoid hydrocarbons are present in bitumen A (C14 - C21; 198 p.p.m.), bitumen B (C15 - C20; 11 p.p.m.), bitumen C (C15 - C23; 157 p.p.m.) and bitumen D (C16, C18 - C23; 515 p.p.m.) 3. (3) Normal alkanes are present in bitumen A (

Capillary gas chromatography mass spectrometry combined by molecular separators applied to methane pyrolysis product analysis

The extractable aliphatic hydrocarbons of several meteorite specimens (carbonaceous chondrites and graphite-troilite nodules of iron meteorites) as well as several terrestrial graphites were separated and identified by the combination of gas chromatography—mass spectrometry. Due to the extreme complexity of the hydrocarbons in these samples and the very low levels of concentration in which the individual components are present, unequivocal structural assignments can only be obtained by means of their respective mass spectral features. From the mass spectrometric patterns eleven homologous series of aliphatic hydrocarbons have been identified. These include the n-alkane series, two isoprenoid series of 2,6,10-trimethyl- and 2,6,10,14-tetramethyl-alkanes, five series of monomethyl substituted alkanes (2-, 3-, 4-, 5-, 6-methylalkanes), one of 4,8-dimethylalkanes, and two of monocycloalkanes (cyclohexyl and cyclopentyl). From the data obtained we can establish interesting correlations between the two types of samples, terrestrial and extraterrestrial, and also determine whether these compounds were derived from biological or abiological sources. The evidence points to possible terrestrial contamination of the meteoritic materials by contact with dust, air or petroleum fumes.

Iron meteorites graphite-troilite nodules isomeric alkane composition, using gas chromatography and mass spectrometry