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      Meteorite-catalyzed syntheses of nucleosides and of other prebiotic compounds from formamide under proton irradiation.

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          Abstract

          Liquid formamide has been irradiated by high-energy proton beams in the presence of powdered meteorites, and the products of the catalyzed resulting syntheses were analyzed by mass spectrometry. Relative to the controls (no radiation, or no formamide, or no catalyst), an extremely rich, variegate, and prebiotically relevant panel of compounds was observed. The meteorites tested were representative of the four major classes: iron, stony iron, chondrites, and achondrites. The products obtained were amino acids, carboxylic acids, nucleobases, sugars, and, most notably, four nucleosides: cytidine, uridine, adenosine, and thymidine. In accordance with theoretical studies, the detection of HCN oligomers suggests the occurrence of mechanisms based on the generation of radical cyanide species (CN·) for the synthesis of nucleobases. Given that many of the compounds obtained are key components of extant organisms, these observations contribute to outline plausible exogenous high-energy-based prebiotic scenarios and their possible boundary conditions, as discussed.

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          Synthesis of activated pyrimidine ribonucleotides in prebiotically plausible conditions.

          At some stage in the origin of life, an informational polymer must have arisen by purely chemical means. According to one version of the 'RNA world' hypothesis this polymer was RNA, but attempts to provide experimental support for this have failed. In particular, although there has been some success demonstrating that 'activated' ribonucleotides can polymerize to form RNA, it is far from obvious how such ribonucleotides could have formed from their constituent parts (ribose and nucleobases). Ribose is difficult to form selectively, and the addition of nucleobases to ribose is inefficient in the case of purines and does not occur at all in the case of the canonical pyrimidines. Here we show that activated pyrimidine ribonucleotides can be formed in a short sequence that bypasses free ribose and the nucleobases, and instead proceeds through arabinose amino-oxazoline and anhydronucleoside intermediates. The starting materials for the synthesis-cyanamide, cyanoacetylene, glycolaldehyde, glyceraldehyde and inorganic phosphate-are plausible prebiotic feedstock molecules, and the conditions of the synthesis are consistent with potential early-Earth geochemical models. Although inorganic phosphate is only incorporated into the nucleotides at a late stage of the sequence, its presence from the start is essential as it controls three reactions in the earlier stages by acting as a general acid/base catalyst, a nucleophilic catalyst, a pH buffer and a chemical buffer. For prebiotic reaction sequences, our results highlight the importance of working with mixed chemical systems in which reactants for a particular reaction step can also control other steps.
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            Evidence for life on Earth before 3,800 million years ago.

            It is unknown when life first appeared on Earth. The earliest known microfossils (approximately 3,500 Myr before present) are structurally complex, and if it is assumed that the associated organisms required a long time to develop this degree of complexity, then the existence of life much earlier than this can be argued. But the known examples of crustal rocks older than 3,500 Myr have experienced intense metamorphism, which would have obliterated any fragile microfossils contained therein. It is therefore necessary to search for geochemical evidence of past biotic activity that has been preserved within minerals that are resistant to metamorphism. Here we report ion-microprobe measurements of the carbon-isotope composition of carbonaceous inclusions within grains of apatite (basic calcium phosphate) from the oldest known sediment sequences--a approximately 3,800-Myr-old banded iron formation from the Isua supracrustal belt, West Greenland, and a similar formation from the nearby Akilia island that is possibly older than 3,850 Myr. The carbon in the carbonaceous inclusions is isotopically light, indicative of biological activity; no known abiotic process can explain the data. Unless some unknown abiotic process exists which is able both to create such isotopically light carbon and then selectively incorporate it into apatite grains, our results provide evidence for the emergence of life on Earth by at least 3,800 Myr before present.
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              Prebiotic chemistry and the origin of the RNA world.

              The demonstration that ribosomal peptide synthesis is a ribozyme-catalyzed reaction makes it almost certain that there was once an RNA World. The central problem for origin-of-life studies, therefore, is to understand how a protein-free RNA World became established on the primitive Earth. We first review the literature on the prebiotic synthesis of the nucleotides, the nonenzymatic synthesis and copying of polynucleotides, and the selection of ribozyme catalysts of a kind that might have facilitated polynucleotide replication. This leads to a brief outline of the Molecular Biologists' Dream, an optimistic scenario for the origin of the RNA World. In the second part of the review we point out the many unresolved problems presented by the Molecular Biologists' Dream. This in turn leads to a discussion of genetic systems simpler than RNA that might have "invented" RNA. Finally, we review studies of prebiotic membrane formation.
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                Author and article information

                Journal
                Proc. Natl. Acad. Sci. U.S.A.
                Proceedings of the National Academy of Sciences of the United States of America
                1091-6490
                0027-8424
                May 26 2015
                : 112
                : 21
                Affiliations
                [1 ] Dipartimento di Scienze Ecologiche e Biologiche, Università della Tuscia, 01100 Viterbo, Italy; ernesto.dimauro@uniroma1.it saladino@unitus.it.
                [2 ] Dipartimento di Scienze Ecologiche e Biologiche, Università della Tuscia, 01100 Viterbo, Italy;
                [3 ] Laboratory of Radiation Biology, Joint Institute for Nuclear Research, 141980 Dubna, Russia; and.
                [4 ] Istituto Pasteur-Fondazione Cenci Bolognetti, c/o Dipartimento di Biologia e Biotecnologie "Charles Darwin," Sapienza-Università di Roma, Rome 00185, Italy ernesto.dimauro@uniroma1.it saladino@unitus.it.
                Article
                1422225112
                10.1073/pnas.1422225112
                25870268
                a6a075c4-4173-432c-85f3-5e5ce730b63f
                History

                formamide,meteorites,nucleosides,origin of life,prebiotic syntheses

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