Selective Phosphonylation of 5'-Adenosine Monophosphate (5'-AMP) via Pyrophosphite [PPi(III)].

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.

Phosphate Activation via Reduced Oxidation State Phosphorus (P). Mild Routes to Condensed-P Energy Currency Molecules.

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.

On the prebiotic potential of reduced oxidation state phosphorus: the H-phosphinate-pyruvate system.

H-Phosphinic acid and pyruvic acid, both plausible prebiotic chemicals, react selectively in water to build structural complexity including amide bond formation under remarkably mild conditions and oxidative coupling of P(1) compounds to condensed pyrophosphorus compounds.

Direct evidence for the availability of reactive, water soluble phosphorus on the early Earth. H-phosphinic acid from the Nantan meteorite.

Anoxic irradiation of a type IIICD iron meteorite known to contain the phosphide mineral schreibersite (Fe,Ni)3P in the presence of ethanol/water affords the reactive oxyacid H-phosphinic acid (H3PO2) as the dominant phosphorus product.

On the origin of the Murchison meteorite phosphonates. Implications for pre-biotic chemistry.

Ab initio calculations, combined with experimental studies on the anaerobic hydrolysis of phosphaalkynes under thermal and photochemical conditions suggest a potential, exogenous source of reduced oxidation state phosphorus for the early Earth.

Performance of three resin-based materials for treating uranium-contaminated groundwater within a PRB.

Three materials that are designed to treat uranium-contaminated water were investigated. These are a cation exchange resin, IRN 77; an anion exchange resin, Varion AP; and a recently developed material called PANSIL (quartz sand coated with 2% amidoxime resin by weight). The reaction rate, capacity, and effective pH range of the three materials are reported. The capacity and conditional distribution coefficient in neutral, uranyl-contaminated synthetic groundwater containing carbonate are also reported. The suitability of each material for treating uranium-contaminated groundwater using a permeable reactive barrier (PRB) approach is then discussed. All three materials react rapidly in the pH range 5-7, reaching equilibrium in less than 4h at approximately 23 degrees C. The unconditioned cation exchange resin removed 8 g UO2 2+ per kg of resin from neutral synthetic groundwater containing 30 mg/l of UO2 2+, but a lower capacity is anticipated in groundwater with either higher ionic strength or lower UO2 2 concentrations. It operates by first acidifying the solution, then sorbing UO2 2, and can release UO2 2 when its buffering capacity has been exhausted. The anion exchange resin is very effective at removing anionic uranyl carbonate species from solutions with a pH above 5, with good specificity. Up to 50 g/kg of uranium is removed from contaminated groundwater at neutral pH. PANSIL is effective at sequestering cationic and neutral uranyl species from solutions in the pH range 4.5-7.5, with very good specificity. The capacity of PANSIL is pH-dependent, increasing from about 0.4 g/kg at pH 4.5, to about 1 g/kg at pH 6, and 1.5 g/kg around pH 7.5. In neutral groundwater containing carbonate, both the anion exchange resin and PANSIL exhibit conditional distribution coefficients exceeding 1470 ml/g, which is about an order of magnitude higher than comparable reactive barrier materials reported in the literature.

Development of a functionalized polymer-coated silica for the removal of uranium from groundwater.

A new active material for the treatment of uranium-contaminated groundwater using permeable reactive barriers has been developed. This material, called PANSIL, is an example of a tailored ligand system that selectively removes a contaminant from solution. The active medium in PANSIL is a polyacryloamidoxime resin derived from polyacrylonitrile, which is deposited from solution onto the surface of quartz sand to form a thin film coating. PANSIL is highly effective at sequestering UO2(2+) from solution when the pH is between about 5 and 8 and can preferentially sequester UO2(2+) from solutions that are typical of the groundwater from a mine tailings site, due to the stability of the polyacryloamidoxime uranyl complex formed. Uranium sequestration capacity will depend on the surface area of the sand that is resin coated, but in the batch of PANSIL tested (<2% resin by weight), it exceeds 4000 mg of UO2 per kg of PANSIL at pH 4.5 when the dissolved UO2(2+) concentration is greaterthan 300 mg/L. PANSIL largely retains the permeability and strength of the sand employed and therefore has suitable engineering properties for permeable reactive barrier applications.