Skip to main content
Log in

Pyrophosphate synthesis from phospho(enol)pyruvate catalyzed by precipitated magnesium phosphate with ”enzyme-like” activity

  • Published:
Journal of Molecular Evolution Aims and scope Submit manuscript

Summary

The enzyme-like kinetic properties of precipitated magnesium phosphate as a catalyst for formation of pyrophosphate (PPi) from phospho (enol)pyruvate (PEP) are described. This synthesis occurs at a low temperature (37°C) and represents a model that may help us understand the relevance to chemical evolution of minerals as ancient catalysts whose functions could have been taken over by contemporary enzymes. An insoluble Pi.Mg matrix was formed in a medium with 80% of the water replaced by dimethyl sulfoxide as a way of simulating conditions in a drying pond. Phospho(enol)pyruvate adsorbs onto the Pi.Mg surface according to a Langmuir isotherm, and the PEP concentration dependence of PPi formation follows a Michaelian-like function. A yield of 33% for transformation of the initially adsorbed PEP into PPi was attained after 4 days of incubation with equimolecular concentrations of Pi, MgCl2, and PEP. The magnesium concentration dependence for Pi and Mg precipitation, for adsorption of PEP onto solid Pi.Mg, and for PPi formation showed complex cooperative behavior. These results taken as a whole lead to the conclusion that the Pi.Mg surface not only provides a reactant for PPi formation but also catalyzes the reaction.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Baldwin E (1964) An introduction to comparative biochemistry. Cambridge University Press, Cambridge (UK), pp 13–16

    Google Scholar 

  • Baltscheffsky H, Lundin M, Luxemburg C, Nyrén P, Baltscheffsky M (1986) Inorganic pyrophosphate and the molecular evolution of biological energy coupling. Chem Scr 26B:259–262

    Google Scholar 

  • Bernal JD (1951) The physical basis of life. Routledge and Kegan Paul, London

    Google Scholar 

  • Boyer PD, Bryan DM (1967) The application of 180 methods to oxidative phosphorylation. Methods Enzymol 10:60–71

    Google Scholar 

  • Briggs LI, Pollack HN (1967) Digital model of evaporite sedimentation. Science 155:453–456

    Google Scholar 

  • Burton FG, Neuman MW, Neuman WIT (1969) On the possible role of crystals in the origins of life. I. The adsorption of nucleotides and pyrophosphate by apatite crystals. Curr Mod Biol 3:20–26

    Google Scholar 

  • Cairns-Smith AG (1982) Genetic takeover and the mineral origins of life. Cambridge University Press, London, pp 121–131, 241–243

    Google Scholar 

  • Clegg JS (1984a) Properties and metabolism of the aqueous cytoplasm and its boundaries. Am J Physiol 246:R133-R151

    Google Scholar 

  • Clegg JS (1984b) Intracellular water and the cytomatrix: some methods of study and current views. J Cell Biol 99: 167s-171s

  • Cope FW (1969) Nuclear magnetic resonance evidence using D20 for structural water in muscle and brain. Biophys J 9: 303–319

    Google Scholar 

  • Damadian R (1971) Biological ion exchanger resins. I. Quantitative electrostatic correspondence of fixed charge and mobile counter ion. Biophys J 11:739–760

    Google Scholar 

  • Damadian R, Goldsmith M, Zaner KS (1971) Biological ion exchanger resins. II. QUERP water and ion exchange selectivity. Biophys J 11:761–772

    Google Scholar 

  • Dayhoff MO, Schwarts RM, Orcutt BC (1978) Atlas of protein sequence and structure. Natl Biomed Res Found, Washington DC, pp 345–363

    Google Scholar 

  • de Meis L, Behrens MI, Petretski JH, Politi MJ (1985) Contribution of water to free energy of hydrolysis of pyrophosphate. Biochemistry 24:7783–7789

    Google Scholar 

  • Erskelens J (1990) A comparison of enzymatic and heterogeneous catalysis. Naturwissenschaften 77:86–87

    Google Scholar 

  • Ferris JP (1968) Cyanovinyl phosphate: a prebiological phosphorylating agent. Science 161:53–54

    Google Scholar 

  • Ferris JP, Hagan WJ Jr (1986) The adsorption and reaction of adenine nucleotides on montmorillonite. Origins Life 17:69–84

    Google Scholar 

  • Ferris JP, Huang C-H, Hagan WJ Jr (1988) Montmorillonite: a multifunctional mineral catalyst for the prebiological formation of phosphate esters. Origins Life 18:121–133

    Google Scholar 

  • Fiske CH, SubbaRow Y (1925) The colorimetric determination of phosphorus. J Biol Chem 66:375–400

    Google Scholar 

  • Giles CH, Smith D, Huitson A (1974a) A general treatment and classification of the solute adsorption isotherm. I. Theoretical. J Colloid Interface Sci 47:755–765

    Google Scholar 

  • Giles CH, D'Silva AP, Easton IA (1974b) A general treatment and classification of the solute adsorption isotherm. II. Experimental interpretation. J Colloid Interface Sci 47:766–778

    Google Scholar 

  • Glasstone S, Laidler KJ, Eyring H (1941) The theory of rate processes. McGraw-Hill, New York

    Google Scholar 

  • Hermes-Lima M (1989) Formação de pirofosfato a partir de fosfo(enol)piruvato adsorvido em ortofosfato precipitado: Um modelo para a catálise pre-biótica de transfosforilações. MSc Thesis. Federal University of Rio de Janeiro, Brazil

    Google Scholar 

  • Hermes-Lima M, Vieyra A (1989) Pyrophosphate formation from phospho(enol)pyruvate adsorbed onto precipitated orthophosphate: a model for pre-biotic catalysis of transphosphorylations. Origins Life 19:143–152

    Google Scholar 

  • Hermes-Lima M (1990a) Model for prebiotic pyrophosphate formation: condensation of precipitated orthophosphate at low temperature in the absence of condensing or phosphorylating agents. J Mol Evol 31:353–358

    Google Scholar 

  • Hermes-Lima M (1990b) Natural selection in the RNA-like world. Naturwissenschaften 77:226–227

    Google Scholar 

  • Hermes-Lima M, Tessis AC, Vieyra A (1990) Adsorption of 5′-adenosine monophosphate onto precipitated calcium phosphate: effects of inorganic polyphosphates and carbamyl phosphate. Origins Life 20:27–41

    Google Scholar 

  • Herschlag D, Jencks WP (1986) Pyrophosphate formation from acetyl phosphate and orthophosphate anions in concentrated aqueous salt solutions does not provide evidence for a metaphosphate intermediate. J Am Chem Soc 108:7938–7945

    Google Scholar 

  • Hopkins EAH, Wang JH (1965) Catalysis of phosphoryl group transfer by alkali ions. J Am Chem Soc 87:4391–4392

    Google Scholar 

  • Hulshof J, Ponnamperuma C (1976) Prebiotic condensation reactions in an aqueous medium: a review of condensing agents. Origins Life 7:197–224

    Google Scholar 

  • Jencks WP (1969) Catalysis in chemistry and enzymology. McGraw Hill, New York, pp 40–41

    Google Scholar 

  • Joyce GJ (1989) RNA evolution and the origins of life. Nature 338:217–224

    Google Scholar 

  • Kaunitz H, Johnson RE (1979) Biological effects of salts. J Nutr Sci (Suppl 22): 1–45

  • Kinsman DJJ (1975) Salt floors to geosynclines. Nature 255:375–378

    Google Scholar 

  • Knowles JR (1980) Enzyme-catalyzed phosphoryl transfer reactions. Ann Rev Biochem 49:877–919

    Google Scholar 

  • Krane SM, Glimcher MJ (1962) Transphosphorylation from nucleoside di- and triphosphates by apatite crystals. J Biol Chem 237:2291–2998

    Google Scholar 

  • Lahav N, Chang S (1976) The possible role of solid surface area in condensation reactions during chemical evolution: Reevaluation. J Mol Evol 8:357–380

    Google Scholar 

  • Lahav N, Chang S (1982) The possible role of soluble salts in chemical evolution. J Mol Evol 19:36–46

    Google Scholar 

  • Lowenstein JM (1958) Transphosphorylations catalyzed by bivalent metal ions. Biochem J 70:222–230

    Google Scholar 

  • Meyer-Fernandes JR, Vieyra A (1988) Pyrophosphate formation from acetyl phosphate and orthophosphate: Evidence for heterogeneous catalysis. Arch Biochem Biophys 266:132–141

    Google Scholar 

  • Miller SL, Parris M (1964) Synthesis of pyrophosphate under primitive earth conditions. Nature 204:1248–1250

    Google Scholar 

  • Miller J, Parker AJ (1961) Dipolar aprotic solvents in bimolecular aromatic nucleophilic substitution reactions. J Am Chem Soc 83:117–123

    Google Scholar 

  • Miller DL, Westheimer FH (1966) Interaction of γ-phenylpropyl triphosphate with cations. J Am Chem Soc 88:1514–1517

    Google Scholar 

  • Nelson N, Racker E (1973) Phosphate transfer from adenosine triphosphate in a model system. Biochemistry 12:563–566

    Google Scholar 

  • Neuman MW, Neuman WF, Kane K (1970) On the possible role of crystals in the origins of life. IV. The phosphorylation of nucleotides. Curr Mod Biol 3:277–283

    Google Scholar 

  • Orenberg JB, Chan S, Calderon C, Lahav N (1985) Soluble minerals in chemical evolution. I. Adsorption of 5′-AMP on CaSO4—a model system. Origins Life 15:121–129

    Google Scholar 

  • ParkerAJ (1962) The effects of solvation on the properties of anions in dipolar aprotic solvents. Quart Rev 16:163–187

    Google Scholar 

  • Parker AJ (1967) Rates of bimolecular substitution reactions in protic and dipolar aprotic solvents. Adv Phys Org Chem 5: 173–235

    Google Scholar 

  • Pedersen PL, Carafoli E (1987) Ion motive ATPases. II. Energy coupling and work output. Trends Biochem Sci 12:186–189

    Google Scholar 

  • Pickart CM, Jencks WP (1984) Energetics of the calcium-transporting ATPase. J Biol Chem 259:1629–1643

    Google Scholar 

  • Ponnamperuma C, Shimoyama A, Friebele E (1982) Clays and the origin of life. Origins Life 12:9–40

    Google Scholar 

  • Ramirez F, Marecek JF (1980a) Phosphoryl transfer from phosphomonoesters in aprotic and protic solvents. Pure Appl Chem 52:1021–1045

    Google Scholar 

  • Ramirez F, Marecek JF (1980b) Phosphorylations by adenosine 5′-triphosphate. Pure Appl Chem 52:2213–2227

    Google Scholar 

  • Rao M, Odom DG, Orb J (1980) Clays in prebiological chemistry. J Mol Evol 15:317–331

    Google Scholar 

  • Schaleger LL, Long FA (1963) Entropies of activation and mechanisms of reactions in solutions. Adv Phys Org Chem 1:1–33

    Google Scholar 

  • Shen C, Lazcano A, Orb J (1990) The enhancement activities of histidyl-histidine in some prebiotic reactions. J Mol Evol 31: 445–452

    Google Scholar 

  • Vieyra A (1982) Incremento da reatividade do fosfato inorgânico. Reações de fosforólise em meios com a atividade da água diminuida. PhD Thesis. Federal University of Rio de Janeiro, Brazil

    Google Scholar 

  • Vieyra A, Meyer-Fernandes JR, Gama OBH (1985) Phosphorolysis of acetyl phosphate by orthophosphate with energy conservation in the phosphoanhydride linkage of pyrophosphate. Arch Biochem Biophys 238:574–583

    Google Scholar 

  • Vieyra A, Tessis AC, Vidigal-Zaccaro ME 1991 Non enzymatic synthesis of ADP onto phosphate surfaces: a model far prebiotic catalysis of phosphorylations. Abstracts of the 15th International Congress of Biochemistry. Jerusalem, Israel, August 1991

Download references

Author information

Authors and Affiliations

Authors

Additional information

Offprint requests to: A. Vieyra

Rights and permissions

Reprints and permissions

About this article

Cite this article

Hermes-Lima, M., Vieyra, A. Pyrophosphate synthesis from phospho(enol)pyruvate catalyzed by precipitated magnesium phosphate with ”enzyme-like” activity. J Mol Evol 35, 277–285 (1992). https://doi.org/10.1007/BF00161165

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00161165

Key words

Navigation