Urea-Inorganic Phosphate Mixtures as Prebiotic Phosphorylating Agents

Lohrmann, R.; Orgel, Leslie E.

doi:10.1126/science.171.3970.490

Cited by 224 publications

(124 citation statements)

References 9 publications

Supporting

Mentioning

122

Contrasting

Order By: Relevance

“…Attempts to perform this reaction using inorganic phosphate have only been successful in the presence of heat, urea, and/or formamide (36,37). However, conceptual models of prebiotic RNA synthesis have also invoked phosphite as an important phosphorylating reagent (38).…”

Section: Discussionmentioning

confidence: 99%

Evidence for reactive reduced phosphorus species in the early Archean ocean

Pasek

Harnmeijer

Buick

et al. 2013

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

171

170

View full text Add to dashboard Cite

It has been hypothesized that before the emergence of modern DNA-RNA-protein life, biology evolved from an "RNA world." However, synthesizing RNA and other organophosphates under plausible early Earth conditions has proved difficult, with the incorporation of phosphorus (P) causing a particular problem because phosphate, where most environmental P resides, is relatively insoluble and unreactive. Recently, it has been proposed that during the Hadean-Archean heavy bombardment by extraterrestrial impactors, meteorites would have provided reactive P in the form of the iron-nickel phosphide mineral schreibersite. This reacts in water, releasing soluble and reactive reduced P species, such as phosphite, that could then be readily incorporated into prebiotic molecules. Here, we report the occurrence of phosphite in early Archean marine carbonates at levels indicating that this was an abundant dissolved species in the ocean before 3.5 Ga. Additionally, we show that schreibersite readily reacts with an aqueous solution of glycerol to generate phosphite and the membrane biomolecule glycerol-phosphate under mild thermal conditions, with this synthesis using a mineral source of P. Phosphite derived from schreibersite was, hence, a plausible reagent in the prebiotic synthesis of phosphorylated biomolecules and was also present on the early Earth in quantities large enough to have affected the redox state of P in the ocean. Phosphorylated biomolecules like RNA may, thus, have first formed from the reaction of reduced P species with the prebiotic organic milieu on the early Earth.origin of life | prebiotic chemistry | phosphorylation | astrobiology | exobiology P hosphorus (P) is the limiting nutrient in many ecosystems; its scarcity is linked to the insoluble nature of phosphate minerals (1, 2). Phosphorus species may have been important reagents during prebiotic chemical evolution, but their presumed low abundance has presented a problem in understanding the origin of key phosphorylated biomolecules, such as RNA (3, 4). This was recognized early in the study of prebiotic chemistry, and a possible role for more reduced P compounds was suggested because these are more soluble than phosphate (5, 6). However, no potential source of reduced P was known at the time, leaving phosphate as the only available P species under typical geochemical conditions (7).Phosphide minerals such as schreibersite (Fe,Ni) 3 P are ubiquitous minor constituents of meteorites (8) and are potential sources of reduced P (9-12). Schreibersite reacts with water to release P compounds that are reduced relative to the geologically abundant P 5+ phase phosphate PO 4 3− , including P 3+ phosphite HPO 3 2− and P 1+ hypophosphite H 2 PO 2 − (9-14). Both of these compounds are significantly more soluble than phosphate in waters of neutral pH and rich in the divalent cations Ca 2+ and Mg 2+ , such as modern seawater (5). Schreibersite reaction rates indicate complete phosphide dissolution when submerged in water over about 10 y (12), implying rapid reaction with w...

show abstract

Section: Discussionmentioning

confidence: 99%

Evidence for reactive reduced phosphorus species in the early Archean ocean

Pasek

Harnmeijer

Buick

et al. 2013

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

171

170

View full text Add to dashboard Cite

show abstract

“…Nucleosides can be converted to a complex mixture of products containing one or more phosphate groups in excellent yield by heating at moderate temperatures with ammonium phosphate and urea (Lohrmann & Orgel, 1971). When uridine, for example, is heated with excess urea and ammonium phosphate at 100 • C, about 70% of the input is converted to a complex mixture of phosphorylated products ( Figure 5).…”

Section: Phosphorylation Of Nucleosidesmentioning

confidence: 99%

“…Redrawn from Figure 6 in Lohrmann and Orgel (1971). with urea, ammonium chloride, and a nucleoside at 100 • C (Lohrmann & Orgel, 1971).…”

Section: Phosphorylation Of Nucleosidesmentioning

confidence: 99%

Prebiotic Chemistry and the Origin of the RNA World

Orgel

2004

Critical Reviews in Biochemistry and Molecular Biology

923

248

View full text Add to dashboard Cite

The demonstration that ribosomal peptide synthesis is a ribozyme-catalyzed reaction makes it almost certain that there was once an RNA World. The central problem for origin-of-life studies, therefore, is to understand how a protein-free RNA World became established on the primitive Earth. We first review the literature on the prebiotic synthesis of the nucleotides, the nonenzymatic synthesis and copying of polynucleotides, and the selection of ribozyme catalysts of a kind that might have facilitated polynucleotide replication. This leads to a brief outline of the Molecular Biologists' Dream, an optimistic scenario for the origin of the RNA World. In the second part of the review we point out the many unresolved problems presented by the Molecular Biologists' Dream. This in turn leads to a discussion of genetic systems simpler than RNA that might have "invented" RNA. Finally, we review studies of prebiotic membrane formation.

show abstract

“…Experimentally, there have been several notably successful reactions that ostensibly support this nucleobase ribosylation approach: Orgel's and Miller's syntheses of cytosine 10 (Ferris et al 1968;Robertson and Miller 1995); Benner's and Darbre's syntheses of ribose 3 by aldolization of glycolaldehyde 4 and glyceraldehyde 5 (Ricardo et al 2004;Kofoed et al 2005); Pasek's and Kee's demonstration of phosphate synthesis by disproportionation of meteoritic metal phosphides (Pasek and Lauretta 2005;Bryant and Kee 2006); and Orgel's urea-catalyzed phosphorylation of nucleosides (eg., 11 (BvC)!2 (BvC)) (Lohrmann and Orgel 1971). Indeed, for many years, a prebiotically plausible synthesis of ribonucleotides from ribose 3, the nucleobases, and phosphate has been tantalizingly close but for one step of the assumed synthesis-the joining of ribose to the nucleobases.…”

mentioning

confidence: 99%

Ribonucleotides

Sutherland

2010

Cold Spring Harbor Perspectives in Biology

View full text Add to dashboard Cite

It has normally been assumed that ribonucleotides arose on the early Earth through a process in which ribose, the nucleobases, and phosphate became conjoined. However, under plausible prebiotic conditions, condensation of nucleobases with ribose to give b-ribonucleosides is fraught with difficulties. The reaction with purine nucleobases is low-yielding and the reaction with the canonical pyrimidine nucleobases does not work at all. The reasons for these difficulties are considered and an alternative high-yielding synthesis of pyrimidine nucleotides is discussed. Fitting the new synthesis to a plausible geochemical scenario is a remaining challenge but the prospects appear good. Discovery of an improved method of purine synthesis, and an efficient means of stringing activated nucleotides together, will provide underpinning support to those theories that posit a central role for RNA in the origins of life.

show abstract

Urea-Inorganic Phosphate Mixtures as Prebiotic Phosphorylating Agents

Cited by 224 publications

References 9 publications

Evidence for reactive reduced phosphorus species in the early Archean ocean

Evidence for reactive reduced phosphorus species in the early Archean ocean

Prebiotic Chemistry and the Origin of the RNA World

Ribonucleotides

Contact Info

Product

Resources

About