title: Amino Acid-Specific, Ribonucleotide-Promoted Peptide Formation in the Absence of Enzymes.
abstract: Nucleic acids and polypeptides are at the heart of life. It is interesting to ask whether the monomers of these biopolymers possess intrinsic reactivity that favors oligomerization in the absence of enzymes. We have recently observed that covalently linked peptido RNA chains form when mixtures of monomers react in salt-rich condensation buffer. Here, we report the results of a screen of the 20 proteinogenic amino acids and four ribonucleotides. None of the amino acids prevent phosphodiester formation, so all of them are compatible with genetic encoding through RNA chain growth. A reactivity landscape was found, in which peptide formation strongly depends on the structure of the amino acid, but less on the nucleobase. For example, proline gives ribonucleotide-bound peptides most readily, tyrosine favors pyrophosphate and phosphodiester formation, and histidine gives phosphorimidazolides as dominant products. When proline and aspartic acid were allowed to compete for incorporation, only proline was found at the N-terminus of peptido chains. The reactivity described here links two fundamental classes of biomolecules through reactions that occur without enzymes, but with amino acid specificity.
authors.affiliation: Institut für Organische Chemie, Universität Stuttgart, 70569, Stuttgart, Germany.
authors.forename: Helmut
authors.initials: H
authors.lastname: Griesser
authors.affiliation: Institut für Organische Chemie, Universität Stuttgart, 70569, Stuttgart, Germany.
authors.forename: Maren
authors.initials: M
authors.lastname: Bechthold
authors.affiliation: Institut für Organische Chemie, Universität Stuttgart, 70569, Stuttgart, Germany.
authors.forename: Peter
authors.initials: P
authors.lastname: Tremmel
authors.affiliation: Institut für Organische Chemie, Universität Stuttgart, 70569, Stuttgart, Germany.
authors.forename: Eric
authors.initials: E
authors.lastname: Kervio
authors.affiliation: Institut für Organische Chemie, Universität Stuttgart, 70569, Stuttgart, Germany.
authors.forename: Clemens
authors.initials: C
authors.lastname: Richert
mesh_terms: D000596:Amino Acids / Q000378:metabolism*; D011756:Diphosphates / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D010455:Peptides / Q000378:metabolism*; D012313:RNA / Q000378:metabolism; D012265:Ribonucleotides / Q000737:chemistry / Q000378:metabolism*
chemical_list: D000596:Amino Acids; D011756:Diphosphates; D010455:Peptides; D012265:Ribonucleotides; D012313:RNA
keywords: RNA; amino acids; nucleotides; peptides; prebiotic chemistry