Reduced-oxidation-state phosphorus (reduced P, hereafter) compounds were likely available on the early Earth via meteorites or through various geologic processes. Due to their reactivity and high solubility, these compounds could have played a significant role in the origin of various organophosphorus compounds of biochemical significance. In the present work, we study the reactions between reduced P compounds and their oxidation products, with the three nucleosides (uridine, adenosine, and cytidine), with organic alcohols (glycerol and ethanolamine), and with the tertiary ammonium organic compound, choline chloride.
View Article and Find Full Text PDFThe in-fall of meteorites and interstellar dust particles during the Hadean-Archean heavy bombardment may have provided the early Earth with various reduced oxidation state phosphorus compounds and minerals, including phosphite (HPO)([Pi(III)]). The ion phosphite ([Pi(III)])has been postulated to be ubiquitous on the early Earth and consequently could have played a role in the emergence of organophosphorus compounds and other prebiotically relevant P species such as condensed P compounds, e.g.
View Article and Find Full Text PDFPhosphate minerals such as those in the apatite group tend to be the dominant forms of phosphorus in minerals on the Earth's surface. Phosphate can be reduced to phosphides during high-energy events, such as lightning and impacts. Here we show that, in addition to formation of metal phosphides, a new compound was formed by lightning in a fulgurite from New Port Richey, Florida, USA.
View Article and Find Full Text PDFProc Natl Acad Sci U S A
January 2023
We report the discovery of a dodecagonal quasicrystal MnSiCrAlNi-composed of a periodic stacking of atomic planes with quasiperiodic translational order and 12-fold symmetry along the two directions perpendicular to the planes-accidentally formed by an electrical discharge event in an eolian dune in the Sand Hills near Hyannis, Nebraska, United States. The quasicrystal, coexisting with a cubic crystalline phase with composition MnSiNiCrAl, was found in a fulgurite consisting predominantly of fused and melted sand along with traces of melted conductor metal from a nearby downed power line. The fulgurite may have been created by a lightning strike that combined sand with material from downed power line or from electrical discharges from the downed power line alone.
View Article and Find Full Text PDFPhosphorus (P) is a crucial structural component of living systems and central to modern bioenergetics. P cycles through terrestrial geochemical reservoirs via complex physical and chemical processes. Terrestrial life has altered these fluxes between reservoirs as it evolved, which is why it is of interest to explore planetary P flux evolution in the absence of biology.
View Article and Find Full Text PDFLife is a complex, open chemical system that must be supported with energy inputs. If one fathoms how simple early life must have been, the complexity of modern-day life is staggering by comparison. A minimally complex system that could plausibly provide pyrophosphates for early life could be the oxidation of reduced phosphorus sources such as hypophosphite and phosphite.
View Article and Find Full Text PDFThe possibility of life in the venusian clouds was proposed in the 1960s, and recently this hypothesis has been revived with the potential detection of phosphine (PH) in Venus' atmosphere. These observations may have detected ∼5-20 ppb phosphine on Venus (Greaves , 2020), which raises questions about venusian atmospheric/geochemical processes and suggests that this phosphine could possibly be generated by biological processes. In such a claim, it is essential to understand the abiotic phosphorus chemistry that may occur under Venus-relevant conditions, particularly those processes that may result in phosphine generation.
View Article and Find Full Text PDFHypervelocity impacts can produce features in zircon that are not normally produced by endogenic processes. However, lightning can also induce extreme pressure-temperature excursions, and its effect on zircon has not been studied. With the aim to recognise features that form in response to extreme pressure-temperature excursions but are not unique to hypervelocity impacts, we imaged and undertook microstructural characterization of zircon in a fulgurite (a tubular body of glass and fused clasts that formed in response to a lightning strike).
View Article and Find Full Text PDFSugars are essential for the formation of genetic elements such as RNA and as an energy/food source. Thus, the formose reaction, which autocatalytically generates a multitude of sugars from formaldehyde, has been viewed as a potentially important prebiotic source of biomolecules at the origins of life. When analyzing our formose solutions we find that many of the chemical species are simple carboxylic acids, including α-hydroxy acids, associated with metabolism.
View Article and Find Full Text PDFThe availability of nucleotides on the early Earth is of great significance for the origin of a self-replicating system capable of undergoing evolution. We hereby report the successful phosphorylation reactions of the nucleoside uridine under heating in the "drying pool" prebiotic model at temperatures ranging from 60-75 °C, and by using pyrophosphate as a phosphorylation agent. Uridine monophosphates (UMP) such as uridine-5'-monophosphate (5'-UMP), 2'-UMP, and 3'-UMP, as well as cyclic 2'-3'-UMP, were identified by P-NMR.
View Article and Find Full Text PDFThe numerous and varied roles of phosphorylated organic molecules in biochemistry suggest they may have been important to the origin of life. The prominence of phosphorylated molecules presents a conundrum given that phosphorylation is a thermodynamically unfavorable, endergonic process in water, and most natural sources of phosphate are poorly soluble. We recently demonstrated that a semi-aqueous solvent consisting of urea, ammonium formate, and water (UAFW) supports the dissolution of phosphate and the phosphorylation of nucleosides.
View Article and Find Full Text PDFThe question of where life originated has been contentious for a very long time. Scientists have invoked many environments to address this question. Often, we find ourselves beholden to a location, especially if we think life originated once and then evolved into the myriad forms we now know today.
View Article and Find Full Text PDFThe formation of organophosphate molecules by prebiotic processes relies on nonenzymatic synthesis. Given the centrality of phosphorylated biomolecules in metabolic, structural, and replicative processes, it is highly likely that such nonenzymatic synthesis had to occur early in Earth's history. This Review collects and uses thermodynamic data to constrain processes that may have produced organophosphates and evaluates both the plausibility of reactants and the likelihood that environments conducive to phosphorylation were present.
View Article and Find Full Text PDFOrganophosphates were likely an important class of prebiotic molecules. However, their presence on the early Earth is strongly debated because the low availability of phosphate, which is generally assumed to have been sequestered in insoluble calcium and iron minerals, is widely viewed as a major barrier to organophosphate generation. Herein, we demonstrate that cyanide (an essential prebiotic precursor) and urea-based solvents could promote nucleoside phosphorylation by transforming insoluble phosphate minerals in a "warm little pond" scenario into more soluble and reactive species.
View Article and Find Full Text PDFPhosphorus is a minor element that controls the formation of several key planetary minerals. It is also an element critical to the development of life. A common assumption of phosphorus chemistry is that at low temperatures, phosphorus would have been a volatile component of ices or gases in the outer Solar System.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
June 2019
Phosphorylation of (pre)biotically relevant molecules in aqueous medium has recently been demonstrated using water-soluble diamidophosphate (DAP). Questions arise relating to the prebiotic availability of DAP and other amidophosphosphorus species on the early earth. Herein, we demonstrate that DAP and other amino-derivatives of phosphates/phosphite are generated when Fe P (proxy for mineral schreibersite), condensed phosphates, and reduced oxidation state phosphorus compounds, which could have been available on early earth, are exposed to aqueous ammonia solutions.
View Article and Find Full Text PDFPhosphorus is a major biogeochemical element controlling growth in many ecosystems. It has presumably been an important element since the onset of life. In most chemical and biochemical considerations, phosphorus is synonymous with phosphates, a pentavalent oxidation state that includes the phosphate backbone of DNA and RNA, as well as major metabolites such as ATP.
View Article and Find Full Text PDFA hypothesis in prebiotic chemistry argues that organics were delivered to the early Earth in abundance by meteoritic sources. This study tests that hypothesis by measuring how the transfer of organic matter to the surface of Earth is affected by energy-dissipation processes such as ablation and airbursts. Exogenous delivery has been relied upon as a source of primordial material, but it must stand to reason that other avenues (i.
View Article and Find Full Text PDFThe element phosphorus (P) is central to ecosystem growth and is proposed to be a limiting nutrient for life. The Archean ocean may have been strongly phosphorus-limited due to the selective binding of phosphate to iron oxyhydroxide. Here we report a new route to solubilizing phosphorus in the ancient oceans: reduction of phosphate to phosphite by iron(II) at low (<200 °C) diagenetic temperatures.
View Article and Find Full Text PDFPhosphorylation reactions of glycerol were studied using different inorganic phosphates such as sodium phosphate, trimetaphosphate (a condensed phosphate), and struvite. The reactions were carried out in two non-aqueous solvents: formamide and a eutectic solvent consisting of choline-chloride and glycerol in a ratio of 1:2.5.
View Article and Find Full Text PDFThe poor reactivity of insoluble phosphates, such as apatite-group minerals, has been a long-appreciated obstacle for proposed models of prebiotic organophosphate formation. This obstacle presents a significant challenge to the nascent development of an RNA world and other models for the origins of life on Earth. Herein, we demonstrate that a scenario based on the formation of a urea/ammonium formate/water (UAFW) eutectic solution leads to an increase in phosphorylation when compared to urea alone for phosphate sources of varying solubility.
View Article and Find Full Text PDFWhen lightning strikes soil, it may generate a cylindrical tube of glass known as a fulgurite. The morphology of a fulgurite is ultimately a consequence of the energy of the lightning strike that formed it, and hence fulgurites may be useful in elucidating the energy distribution frequency of cloud-to-ground lightning. Fulgurites from sand mines in Polk County, Florida, USA were collected and analyzed to determine morphologic properties.
View Article and Find Full Text PDFWe present a study of the reactions of the meteoritic mineral schreibersite (Fe,Ni)3P, focusing primarily on surface chemistry and prebiotic phosphorylation. In this work, a synthetic analogue of the mineral was synthesized by mixing stoichiometric proportions of elemental iron, nickel and phosphorus and heating in a tube furnace at 820 °C for approximately 235 hours under argon or under vacuum, a modification of the method of Skála and Drábek (2002). Once synthesized, the schreibersite was characterized to confirm the identity of the product as well as to elucidate the oxidation processes affecting the surface.
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