Potentially prebiotic syntheses of condensed phosphates

Keefe, Anthony D.; Miller, Stanley L.

doi:10.1007/bf01808157

Cited by 29 publications

(20 citation statements)

References 34 publications

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“…Cyanoguanidine (a dimer of cyanamide) gave a 1.8% conversion to pyrophosphate in the presence of kaolinite, but only under acidic (pH<2) conditions and 0.1 M concentrations of both reactants (Steinman et al 1965). Condensing agents investigated by Keefe and Miller (1996) that were effective in the synthesis of pyrophosphate include maleic anhydride, pantoyl lactone and ammonium formate, but these are noteworthy for the use of high concentrations (0.25 M) and high temperatures (100°C) that render the syntheses implausible; of particular interest was a mixture of thiocyanate, hydrogen peroxide and phosphate, which gave efficient conversion to pyrophosphate under milder conditions, but as Keefe and Miller noted, the yields are too sensitive to the ratio of the reagents to regard it as "robust." Thioesters such as N, S-diacetylcysteamine are compelling because of their relevance to modern metabolism, but the prebiotic importance to the formation of pyrophosphate is diminished by the high concentrations: 0.1-0.2 M for the thioester, 0.2-0.4 M for the imidazole catalyst and 0.08-0.4 M for inorganic phosphate (Weber 1981(Weber , 1982.…”

Section: Relevance To Prebiotic Chemistrymentioning

confidence: 99%

Phosphate Solubility and the Cyanate-Mediated Synthesis of Pyrophosphate

Hagan

Parker

Steuerwald

et al. 2006

Orig Life Evol Biosph

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The justification for a less alkaline primordial ocean (than present) is briefly reviewed, along with constraints on aqueous phosphate under such conditions. Based on the assumption that CaHPO(4) dihydrate determined the availability of phosphorus species, we have carried out laboratory simulations to determine equilibrium concentrations as a function of pH (in PIPES buffer) with added NaCl and CaCl(2). Consistent with expectations, solubility declines with higher pH and [CaCl(2)], but increases only slightly with [NaCl]. Significantly, PIPES shows no specific effect on the dissolution beyond its influence on pH and ionic strength. Data are also presented on the synthesis of pyrophosphate from the NaOCN/CaHPO(4).2H(2)O system, which could have provided a source of this phosphate anhydride on the early Earth.

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Section: Relevance To Prebiotic Chemistrymentioning

confidence: 99%

Phosphate Solubility and the Cyanate-Mediated Synthesis of Pyrophosphate

Hagan

Parker

Steuerwald

et al. 2006

Orig Life Evol Biosph

View full text Add to dashboard Cite

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“…Most models for prebiotic syntheses of condensed phosphates are characterized by low yields or forced conditions (Yamagata et al, 1991;Keefe and Miller, 1996): involving some combination of high temperatures (ϾϾ100 o C); abiological dehydrating agents; and/or drying cycles to increase polyphosphate yields, in contradistinction to reactions taking place at moderate temperatures in a fully aqueous environment. In addition, many of these syntheses have no counterpart in extant biochemistry and hence would present unwelcome discontinuities in the emergence of metabolism.…”

Section: Introductionmentioning

confidence: 99%

Biomimetic phosphoryl transfer catalysed by iron(II)-mineral precipitates

Zwart

Meade

Pratt

2004

Geochimica et Cosmochimica Acta

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“…The predecessors of the latter enzymes probably used oligophosphates, the presumed energy-rich phosphate compounds during prebiotic evolution (39,40), to phosphorylate early nucleotidelike molecules. This assumption is supported by the finding that, similar to HprK͞P, adenylate kinase also can use tripolyphosphate as phosphoryl donor (41).…”

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confidence: 99%

Pyrophosphate-producing protein dephosphorylation by HPr kinase/phosphorylase: A relic of early life?

Mijaković

Poncet

Galinier

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

113

120

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In most Gram-positive bacteria, serine-46-phosphorylated HPr (PSer-HPr) controls the expression of numerous catabolic genes (Ϸ10% of their genome) by acting as catabolite corepressor. HPr kinase͞phosphorylase (HprK͞P), the bifunctional sensor enzyme for catabolite repression, phosphorylates HPr, a phosphocarrier protein of the sugar-transporting phosphoenolpyruvate/glycose phosphotransferase system, in the presence of ATP and fructose-1,6-bisphosphate but dephosphorylates P-Ser-HPr when phosphate prevails over ATP and fructose-1,6-bisphosphate. We demonstrate here that P-Ser-HPr dephosphorylation leads to the formation of HPr and pyrophosphate. HprK͞P, which binds phosphate at the same site as the ␤ phosphate of ATP, probably uses the inorganic phosphate to carry out a nucleophilic attack on the phosphoryl bond in P-Ser-HPr. HprK͞P is the first enzyme known to catalyze P-protein dephosphorylation via this phosphophosphorolysis mechanism. This reaction is reversible, and at elevated pyrophosphate concentrations, HprK͞P can use pyrophosphate to phosphorylate HPr. Growth of Bacillus subtilis on glucose increased intracellular pyrophosphate to concentrations (Ϸ6 mM), which in in vitro tests allowed efficient pyrophosphatedependent HPr phosphorylation. To effectively dephosphorylate P-Ser-HPr when glucose is exhausted, the pyrophosphate concentration in the cells is lowered to 1 mM. In B. subtilis, this might be achieved by YvoE. This protein exhibits pyrophosphatase activity, and its gene is organized in an operon with hprK.

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Potentially prebiotic syntheses of condensed phosphates

Abstract: Abstract.In

Cited by 29 publications

References 34 publications

Phosphate Solubility and the Cyanate-Mediated Synthesis of Pyrophosphate

Phosphate Solubility and the Cyanate-Mediated Synthesis of Pyrophosphate

Biomimetic phosphoryl transfer catalysed by iron(II)-mineral precipitates

Pyrophosphate-producing protein dephosphorylation by HPr kinase/phosphorylase: A relic of early life?

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