A radical pathway for organic phosphorylation during schreibersite corrosion with implications for the origin of life

Pasek, Matthew A.; Dworkin, Jason P.; Лауретта, Д. С.

doi:10.1016/j.gca.2006.12.018

Cited by 120 publications

(131 citation statements)

References 42 publications

(49 reference statements)

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“…Acetate reacts with schreibersite to form C-P compounds like acetylphosphonate and hydroxymethylphosphonate, and potentially some C-O-P compounds including phosphoglycolate. The most likely reaction pathway is through a phosphite radical ( • PO 3 2Ϫ ) reacting with an organic radical, as evidenced although electron paramagnetic resonance spectroscopy and other data (35).…”

Section: Phosphorus In the Origin Of Lifementioning

confidence: 95%

“…Each solution was analyzed by using 31 P NMR on a Varian 300 four-nucleus probe Fourier transform-NMR (FT-NMR spectrometer at 121.43 MHz and 24.5°C for 256 -35,000 scans after prior work (33,35). Spectra were acquired in both 1 H-decoupled and coupled modes.…”

Section: Methodsmentioning

confidence: 99%

“…Thus, the majority (95%) of P that fell to the Earth was siderophile P, as schreibersite and similar phosphides. Corrosion of iron meteorites occurs rapidly in seawater (34), and experiments suggest corrosion rates on the order of 0.1-10% of Fe 3P corroding per day for powdered schreibersite (33,35). The concentration of these compounds in the early ocean is determined by dividing the total flux of extraterrestrial reduced P by the mass of the present-day ocean, and assumes complete, rapid corrosion of schreibersite with little oxidative loss, as discussed below.…”

Section: Methodsmentioning

confidence: 99%

“…The primary product of schreibersite oxidation by water is phosphite, HPO 3 2Ϫ , with Ͼ50% of the total aqueous P in this form (33,34). A majority of these P compounds likely originate through free-radical combination reactions (35). These corrosion products would have been available shortly after impact and the steady-state oceanic concentration would have been between 10 Ϫ5 and 10 Ϫ2 moles of reduced P compounds per liter of ocean water.…”

Section: Phosphorus In the Origin Of Lifementioning

confidence: 99%

“…Thus, in a hypothetical early Earth ocean in which P chemistry consisted of both orthophosphate and phosphite, the concentration of phosphite would determine the bulk of dissolved P in the ocean. Phosphite is also much more reactive than orthophosphate, capable of forming condensed phosphates, organic C-P compounds, and even C-O-P compounds (35). Despite its increased reactivity over orthophosphate, phosphite is stable in the absence of strong oxidizing agents and could have persisted on the early Earth in excess of a billion years.…”

Section: Phosphorus In the Origin Of Lifementioning

confidence: 99%

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Rethinking early Earth phosphorus geochemistry

Pasek

2008

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

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Phosphorus is a key biologic element, and a prebiotic pathway leading to its incorporation into biomolecules has been difficult to ascertain. Most potentially prebiotic phosphorylation reactions have relied on orthophosphate as the source of phosphorus. It is suggested here that the geochemistry of phosphorus on the early Earth was instead controlled by reduced oxidation state phosphorus compounds such as phosphite (HPO 3 2؊ ), which are more soluble and reactive than orthophosphates. This reduced oxidation state phosphorus originated from extraterrestrial material that fell during the heavy bombardment period or was produced during impacts, and persisted in the mildly reducing atmosphere. This alternate view of early Earth phosphorus geochemistry provides an unexplored route to the formation of pertinent prebiotic phosphorus compounds, suggests a facile reaction pathway to condensed phosphates, and is consistent with the biochemical usage of reduced oxidation state phosphorus compounds in life today. Possible studies are suggested that may detect reduced oxidation state phosphorus compounds in ancient Archean rocks.meteorites ͉ origins of life ͉ phosphonates ͉ prebiotic ͉ redox chemistry P hosphorus (P) is a key biologic element and is the limiting reagent in many ecosystems. Phosphorus is ubiquitous in biochemistry because phosphorylated biomolecules play major roles in replication and information (as RNA and DNA), metabolism (as ATP, NADPH, and other coenzymes), and structure (as phospholipids). Several key properties of P as phosphate make it advantageous to biologic systems, including thermodynamic instability coupled with kinetic stability, charge and coordination state, and a constant oxidation state under typical redox conditions (1). These features are especially critical to the formation of large informational polymers, and hence highly relevant to the origin and development of early life. Phosphorus Geochemistry and CosmochemistryThe major forms of P in life are summarized in Fig. 1. Inorganic P compounds used by life include orthophosphate, pyrophosphate and other condensed phosphates, phosphite, hypophosphite, and phosphine. These inorganic forms are either used by organisms as sources of P for the synthesis of organic-P biomolecules or are possible metabolic by-products of P metabolism (PH 3 ). Additionally, orthophosphate acts as a buffer in many cells, keeping pH constant at Ϸ7. Organic forms of P include compounds with C-O-P linkages and compounds with C-P linkages, and both are formed from inorganic P by using enzymes.Phosphorus is a lithophile element at the redox conditions on the surface of the Earth, and hence orthophosphate is the dominant form of inorganic P on the surface of the Earth today. The concentration of orthophosphate is water-buffered by the solubility of orthophosphate minerals like apatite, Ca 5 (PO 4 ) 3 (OH,F,Cl), on the present-day Earth, and of whitlockite, Ca 9 MgH(PO 4 ) 7 , and brushite, CaHPO 4 ⅐2H 2 O, before the rise of life-mediated apatite deposition (2). Because ...

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Section: Phosphorus In the Origin Of Lifementioning

confidence: 95%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Phosphorus In the Origin Of Lifementioning

confidence: 99%

Section: Phosphorus In the Origin Of Lifementioning

confidence: 99%

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Rethinking early Earth phosphorus geochemistry

Pasek

2008

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

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235

209

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Origins of Life: Emergence of the RNA World

Robertson

2008

Wiley Encyclopedia of Chemical Biology

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The RNA World hypothesis refers to a period during the evolution of life on Earth, preceding the DNA/RNA/protein‐based systems of modern biology, during which RNA alone directed and catalyzed the chemistry of life. The concept is an elegant solution to the problem of devolving our intertwined 3‐biopolymer biochemistry toward its origins as the simplest system imaginable. In support of this idea, a scattering of molecular clues within our cells point suggestively toward an RNA‐only period leading up to the ribozyme‐mediated invention of protein synthesis. Indeed, the RNA World hypothesis is a very sensible scenario when considered from the perspective of trying to simplify life's complexity. The alternative perspective, however, imagining a sterile, primordial Earth and trying to assemble abiotically produced precursors into the RNA World is an extremely difficult problem. Certain steps along the logical chemical pathway to the RNA World have been demonstrated in the laboratory, but many others remain problematic. The exploration of RNA's catalytic properties has been encouraging, but complex ribozymes are extremely scarce in RNA populations. If the RNA World did once exist, it came about by a mechanism that has not yet been adequately elucidated, including the possibility that a different, unknown, biopolymer system may have preceded the RNA World.

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The Origin of Life

Rehder

2010

Chemistry in Space

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A radical pathway for organic phosphorylation during schreibersite corrosion with implications for the origin of life

Cited by 120 publications

References 42 publications

Rethinking early Earth phosphorus geochemistry

Rethinking early Earth phosphorus geochemistry

Origins of Life: Emergence of the RNA World

The Origin of Life

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