title: Selective Phosphonylation of 5'-Adenosine Monophosphate (5'-AMP) via Pyrophosphite [PPi(III)].
abstract: We describe here experiments which demonstrate the selective phospho-transfer from a plausibly prebiotic condensed phosphorus (P) salt, pyrophosphite [H2P2O52-; PPi(III)], to the phosphate group of 5'-adenosine mono phosphate (5'-AMP). We show further that this P-transfer process is accelerated both by divalent metal ions (M2+) and by organic co-factors such as acetate (AcO-). In this specific case of P-transfer from PPi(III) to 5'-AMP, we show a synergistic enhancement of transfer in the combined presence of M2+& AcO-. Isotopic labelling studies demonstrate that hydrolysis of the phosphonylated 5'-AMP, [P(III)P(V)-5'-AMP], proceeds via nuceophilic attack of water at the Pi(III) terminus.
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK.|Chemistry Faculty of Natural & Environmental Sciences, University of Southampton, Highfield Southampton, SO17 1BJ, UK.
authors.forename: Karl
authors.initials: K
authors.lastname: Kaye
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK.
authors.forename: David E
authors.initials: DE
authors.lastname: Bryant
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK.|School of Chemistry, University of Glasgow, Joseph Black Building, University Avenue, Glasgow, G12 8QQ, UK.
authors.forename: Katie E R
authors.initials: KE
authors.lastname: Marriott
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK.
authors.forename: Shohei
authors.initials: S
authors.lastname: Ohara
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK.
authors.forename: Colin W G
authors.initials: CW
authors.lastname: Fishwick
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK. t.p.kee@leeds.ac.uk.
authors.forename: Terence P
authors.initials: TP
authors.lastname: Kee
mesh_terms: D000249:Adenosine Monophosphate / Q000737:chemistry*; D002413:Cations, Divalent / Q000737:chemistry*; D008670:Metals; D000069497:Origin of Life; D017553:Phosphorus Compounds / Q000737:chemistry*
chemical_list: D002413:Cations, Divalent; D008670:Metals; D017553:Phosphorus Compounds; D000249:Adenosine Monophosphate
keywords: Nucleotides; Origin of Life; Phosphorus; Prebiotic Chemistry