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Phosphate Activation via Reduced Oxidation State Phosphorus (P). Mild Routes to Condensed-P Energy Currency Molecules
School of Chemistry, University of Leeds, Woodhouse Lane, Leeds, LS2 9JT, UK
Department of Geology, University of South Florida, 4202 East Fowler Ave., SCA 528, Tampa, FL 33620, USA
Department of Earth and Planetary Science, Birkbeck College, University of London, Gower Street, London, WC1E 6BT, UK
UK Centre for Astrobiology, School of Physics and Astronomy, University of Edinburgh, Edinburgh, EH9 3JZ, UK
* Author to whom correspondence should be addressed.
Received: 14 May 2013; in revised form: 8 June 2013 / Accepted: 13 June 2013 / Published: 19 July 2013
Abstract: The emergence of mechanisms for phosphorylating organic and inorganic molecules is a key step en route to the earliest living systems. At the heart of all contemporary biochemical systems reside reactive phosphorus (P) molecules (such as adenosine triphosphate, ATP) as energy currency molecules to drive endergonic metabolic processes and it has been proposed that a predecessor of such molecules could have been pyrophosphate [P2O74−; PPi(V)]. Arguably the most geologically plausible route to PPi(V) is dehydration of orthophosphate, Pi(V), normally a highly endergonic process in the absence of mechanisms for activating Pi(V). One possible solution to this problem recognizes the presence of reactive-P containing mineral phases, such as schreibersite [(Fe,Ni)3P] within meteorites whose abundance on the early Earth would likely have been significant during a putative Hadean-Archean heavy bombardment. Here, we propose that the reduced oxidation state P-oxyacid, H-phosphite [HPO32−; Pi(III)] could have activated Pi(V) towards condensation via the intermediacy of the condensed oxyacid pyrophosphite [H2P2O52−; PPi(III)]. We provide geologically plausible provenance for PPi(III) along with evidence of its ability to activate Pi(V) towards PPi(V) formation under mild conditions (80 °C) in water.
Keywords: phosphorus; prebiotic chemistry; origin of life; meteorites
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Kee, T.P.; Bryant, D.E.; Herschy, B.; Marriott, K.E.R.; Cosgrove, N.E.; Pasek, M.A.; Atlas, Z.D.; Cousins, C.R. Phosphate Activation via Reduced Oxidation State Phosphorus (P). Mild Routes to Condensed-P Energy Currency Molecules. Life 2013, 3, 386-402.
Kee TP, Bryant DE, Herschy B, Marriott KER, Cosgrove NE, Pasek MA, Atlas ZD, Cousins CR. Phosphate Activation via Reduced Oxidation State Phosphorus (P). Mild Routes to Condensed-P Energy Currency Molecules. Life. 2013; 3(3):386-402.
Kee, Terence P.; Bryant, David E.; Herschy, Barry; Marriott, Katie E.R.; Cosgrove, Nichola E.; Pasek, Matthew A.; Atlas, Zachary D.; Cousins, Claire R. 2013. "Phosphate Activation via Reduced Oxidation State Phosphorus (P). Mild Routes to Condensed-P Energy Currency Molecules." Life 3, no. 3: 386-402.