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

Zwart, Icenius I. de; Meade, Susie J.; Pratt, Andrew J.

doi:10.1016/j.gca.2004.01.028

Cited by 44 publications

(39 citation statements)

References 32 publications

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“…There are various proposed geochemical sources for pyrophosphate including formation from the more reduced phosphorus species, phosphite or via volcanic activity and heating . PP i can also be formed by substrate phosphorylation of Ac‐P i and phosphate (P i ) via mineral surface reactions; this has been demonstrated previously in Fe II ‐phosphate precipitates and in Fe–sulfide and Fe–silicate precipitates and membranes . One prebiotic geochemical setting that could likely have facilitated prebiotic mineral‐catalyzed polyphosphate formation and maintained disequilibrium is alkaline hydrothermal vents, where redox, pH, chemical, and thermal gradients would have existed between the seawater and hydrothermal fluid .…”

Section: Introductionmentioning

confidence: 93%

Microfluidic Production of Pyrophosphate Catalyzed by Mineral Membranes with Steep pH Gradients

Wang

Barge

Steinbock

2019

Chemistry A European J

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Pyrophosphate might have functioned as an energy storage/currency molecule on early Earth, essential for the emergence of life. Here we synthesized mineral membranes involving iron(II), iron(III), and other divalent metal cations (calcium, manganese, cobalt, copper, zinc, and nickel) and tested their ability to catalyze the formation of pyrophosphate from phosphate and acetyl phosphate across steep pH gradients in microfluidic devices. We studied the chemical compositions of the precipitate membranes (which included vivianite, goethite, and green rust) using in situ and ex situ micro‐Raman spectroscopy. The yields of pyrophosphate were determined by aqueous 31P NMR spectroscopy. We found that Fe2+ and Ca2+ were the best catalysts for pyrophosphate synthesis among investigated ions; Fe3+ and mixed‐valence iron membranes were also able to promote pyrophosphate formation. In addition, the pH gradients across the membranes affected the pyrophosphate yields and the smallest pH gradient resulted in the highest yield. These results suggest a possible route of substrate phosphorylation in prebiotic hydrothermal systems.

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Section: Introductionmentioning

confidence: 93%

Microfluidic Production of Pyrophosphate Catalyzed by Mineral Membranes with Steep pH Gradients

Wang

Barge

Steinbock

2019

Chemistry A European J

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“…The Mg 2+ is a cofactor of enzymes and an essential catalyst for many biochemical reactions (Yamagata et al , 1995). For instance, polyphosphate generation often has an absolute requirement for divalent metal ions, typically Mg(II) (de Zwart et al , 2004). It is also well known that Mg 2+ is required for the stabilization of the diphosphate group of adenosine diphosphate (ADP) and the triphosphate group of adenosine triphosphate (ATP) (Lindh, 2005).…”

Section: Magnesium As a Catalystmentioning

confidence: 99%

The significance of Mg in prebiotic geochemistry

Holm

2012

Geobiology

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Magnesium plays a special role in biochemistry because of its ability to coordinate six oxygen atoms efficiently in its first coordination shell. Such oxygen atoms may be part of one or two charged oxyanions, which means that Mg2+ can, for instance, tie together two different phosphate groups that are located at distance from each other in a macromolecule, and in this way be responsible for the folding of molecules like RNA. This property of Mg2+ also helps the stabilization of diphosphate and triphosphate groups of nucleotides, as well as promoting the condensation of orthophosphate to oligophosphates, like pyrophosphate and trimetaphosphate. Borates, on the other hand, are known to promote the formation of nucleobases and carbohydrates, ribose in particular, which is yet another constituent of nucleotides. The oldest borate minerals that we find on Earth today are magnesium borates. Dissolved borate stabilizes pentose sugars by forming complexes with cis-hydroxyl groups. In the furanose form of ribose, the preferential binding occurs to the 2 and 3 carbon, leaving the 5 carbon free for phosphorylation. The central role of Mg2+ in the function of ribozymes and its ‘archaic’ position in ribosomes, and the fact that magnesium generally has coordination properties different from other cations, suggests that the inorganic chemistry of magnesium had a key position in the first chemical processes leading to the origin and early evolution of life.

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“…While the importance of heterogeneous catalysis in the cyanate-mediated synthesis of pyrophosphate has been noted by previous authors (Vieyra et al 1995;Beck and Orgel 1965), such studies have employed calcium phosphate precipitates that are not as well characterized as the CaHPO 4 ·2H 2 O used in this work. Similarly, the observation that iron minerals promote pyrophosphate formation at near-neutral pH is a significant finding, but that investigation was restricted to highly activated starting materials, such as phosphoenolpyruvate and acetyl phosphate (De Zwart et al 2004). …”

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

Cited by 44 publications

References 32 publications

Microfluidic Production of Pyrophosphate Catalyzed by Mineral Membranes with Steep pH Gradients

Microfluidic Production of Pyrophosphate Catalyzed by Mineral Membranes with Steep pH Gradients

The significance of Mg in prebiotic geochemistry

Phosphate Solubility and the Cyanate-Mediated Synthesis of Pyrophosphate

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