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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. These reactions were studied in the non-aqueous solvent formamide and in a semi-aqueous solvent comprised of urea: ammonium formate: water (UAFW, hereafter) at temperatures of 55–68 °C. The inorganic P compounds generated through Fenton chemistry readily dissolve in the non-aqueous and semi-aqueous solvents and react with organics to form organophosphites and organophosphates, including those which are identified as phosphate diesters. This dual approach (1) use of non-aqueous and semi-aqueous solvents and (2) use of a reactive inorganic P source to promote phosphorylation and phosphonylation reactions of organics readily promoted anhydrous chemistry and condensation reactions, without requiring any additive, catalyst, or other promoting agent under mild heating conditions. We also present a comparative study of the release of P from various prebiotically relevant phosphate minerals and phosphite salts (e.g., vivianite, apatite, and phosphites of iron and calcium) into formamide and UAFW. These results have direct implications for the origin of biological P compounds from non-aqueous solvents of prebiotic provenance. [ABSTRACT FROM AUTHOR]

Heavy metals like copper and nickel are highly toxic due to their non-biodegradable and carcinogenic nature. In this study, adsorption technique was used to remove these undesired heavy metals from aqueous solutions. Carbon nanotubes (CNTs) due to fascinating member in carbon family are selected as an adsorbent which was further functionalized by citric acid and sulfuric acid. The morphological and structural properties of CNTs before and after functionalization were studied by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM) and energy-dispersive X-ray (EDX) spectroscopy. Batch adsorption method was applied to investigate the adsorption of Cu2+ and Ni2+ ions on bare and acid-functionalized CNTs. The equilibrium concentration of Cu2+ and Ni2+ ions was determined by atomic absorbance spectroscopy. The respective maximum adsorption capacity for Cu2+ ions by CNTs, SA-CNTs and CA-CNTs was 13.19, 25 and 65.35 mg/g, whereas for Ni2+ ions these were 14, 33 and 40 mg/g. The thermodynamic parameters like ΔH, ΔS and ΔG were also calculated by using van't Hoff equation. The adsorption data was compared with the previous findings, and the results showed that acid-functionalized CNTs are more effective than bare CNTs for the adsorption of Cu2+ and Ni2+. Finally, the adsorbent recovery was ensured by desorption study of metal ions by using pre-sorbed Cu2+ and Ni2+ ions. [ABSTRACT FROM AUTHOR]

The 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 (HPO32−)([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., pyrophosphite ([PPi(III)]) and isohypophosphate ([PPi(III–V)]). In the present study, we show that phosphite ([Pi(III)]) oxidizes under mild heating conditions (e.g., wet–dry cycles and a prebiotic scenario mimicking a mildly hot-evaporating/drying pool on the early Earth at 78–83 °C) in the presence of urea and other additives, resulting in changes to orthophosphate ([Pi(V)]) alongside the formation of reactive condensed P compounds (e.g., pyrophosphite ([PPi(III)]) and isohypophosphate ([PPi(III–V)])) through a one-pot mechanism. Additionally, we also show that phosphite ([Pi(III)]) and the condensed P compounds readily react with organics (nucleosides and organic alcohol) to form organophosphorus compounds. [ABSTRACT FROM AUTHOR]

Simple Summary: Phosphorus (P) is essential to life in the form of various phosphate esters that make up DNA, RNA and other cellular structures. It mainly exists in the form of phosphate. However, other reduced-oxidation-state P compounds have also been found in natural waters, in living organisms, and in natural glasses formed by lightning called fulgurites. Iron meteorites often bear a P mineral, schreibersite, which corrodes in water to produce various P species including reduced-oxidation-state compounds such as phosphite. This form of natural P is reactive and unstable as ultimately the phosphides and phosphites convert into phosphate, the most stable form of P on an oxidizing world. Previous analyses of 3.5 billion rocks identified various P species including phosphite revealing that phosphite was present on the early Earth and, despite its reactivity, it was stable under geologic timescales. In the present communication, we present the analyses of a meteoritic sample, the pallasite Seymchan, which is rich in the mineral schreibersite and was allowed to corrode for eight years in water. At room temperature, the schreibersite corroded in water to give P species including phosphate and phosphite. These results indicate that phosphite is not an ephemeral species and it is stable enough to be detected in multiple environments. In-fall of extraterrestrial material including meteorites and interstellar dust particles during the late heavy bombardment are known to have brought substantial amounts of reduced oxidation-state phosphorus to the early Earth in the form of siderophilic minerals, e.g., schreibersite ((FeNi)3P). In this report, we present results on the reaction of meteoritic phosphide minerals in the Seymchan meteorite in ultrapure water for 8 years. The ions produced during schreibersite corrosion (phosphite, hypophosphate, pyrophosphate, and phosphate) are stable and persistent in aqueous solution over this timescale. These results were also compared with the short-term corrosion reactions of the meteoritic mineral schreibersite's synthetic analog Fe3P in aqueous and non-aqueous solutions (ultrapure water and formamide). This finding suggests that the reduced-oxidation-state phosphorus (P) compounds including phosphite could be ubiquitous and stable on the early Earth over a long span of time and such compounds could be readily available on the early Earth. [ABSTRACT FROM AUTHOR]

Phosphorylation 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. The glycerol reacted in formamide and in the eutectic solvent with phosphate to yield its phosphorylated derivatives in the presence of silicates such as quartz sand and kaolinite clay. The reactions were carried out by heating glycerol with a phosphate source at 85 °C for one week and were analyzed by 31P-nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS). The yield of the phosphorylated glycerol was improved by the presence of silicates, and reached 90% in some experiments. Our findings further support the proposal that non-aqueous solvents are advantageous for the prebiotic synthesis of biomolecules, and suggest that silicates may have aided in the formation of organophosphates on the prebiotic earth. [ABSTRACT FROM AUTHOR]

The 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. In addition, under evaporative conditions and in the presence of MgSO4, the UAFW eutectic mobilizes the phosphate sequestered in water-insoluble hydroxyapatite, giving rise to a marked increase in phosphorylation. These results suggest that the prebiotic concentrations of urea in a geologically plausible evaporitic environment could solve the problem of organic phosphorylation on a prebiotic Earth. [ABSTRACT FROM AUTHOR]

We 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. In addition to characterization of the solid product, this schreibersite was reacted with water or with organic solutes in a choline chloride–urea deep eutectic mixture, to constrain potential prebiotic products. Major inorganic solutes produced by reaction of water include orthophosphate, phosphite, pyrophosphate and hypophosphate consistent with prior work on Fe3P corrosion. Additionally, schreibersite corrodes in water and dries down to form a deep eutectic solution, generating phosphorylated products, in this case phosphocholine, using this synthesized schreibersite. [ABSTRACT FROM AUTHOR]

Phosphorus (P) is an essential element for life. It occurs in living beings in the form of phosphate, which is ubiquitous in biochemistry, chiefly in the form of C-O-P (carbon, oxygen and phosphorus), C-P, or P-O-P linkages to form life. Within prebiotic chemistry, several key questions concerning phosphorus chemistry have developed: what were the most likely sources of P on the early Earth? How did it become incorporated into the biological world to form the P compounds that life employs today? Can meteorites be responsible for the delivery of P? What were the most likely solvents on the early Earth and out of those which are favorable for phosphorylation? Or, alternatively, were P compounds most likely produced in relatively dry environments? What were the most suitable temperature conditions for phosphorylation? A route to efficient formation of biological P compounds is still a question that challenges astrobiologists. This article discusses these important issues related to the origin of biological P compounds. [ABSTRACT FROM AUTHOR]

The prebiotic relevance of mineral struvite, MgNH4PO4·6H2O, was studied experimentally as a phosphorylating reagent and, theoretically, to understand the geochemical requirements for its formation. The effectiveness of phosphorylation by the phosphate mineral, monetite, CaHPO4, was also studied to compare to the efficiency of struvite. The experiments focused on the phosphorylation reactions of the minerals with organic compounds, such as nucleosides, glycerol and choline chloride, and heat at 75 °C for about 7-8 days and showed up to 28% phosphorylation of glycerol. In contrast, the compositional requirements for the precipitation of struvite are high ammonium and phosphate concentrations, as well as a little Ca2+ dissolved in the water. Combined, these requirements suggest that it is not likely that struvite was present in excess on the early Earth to carry out phosphorylation reactions. The present study focuses on the thermodynamic aspects of struvite formation, complementing the results given by Orgel and Handschuh (1973), which were based on the kinetic effects. [ABSTRACT FROM AUTHOR]

The second-order non-linear optical (NLO) response of organoimido-substituted hexamolybdates has been tuned from 218.61 × 10-30to 490.10 × 10-30esu. The dipole polarizabilities and second-order nonlinear optical (NLO) properties of organoimido derivatives of hexamolybdates have been investigated by using the time-dependent density functional response theory (TDDFT). The electron withdrawing ability of F (fluorine) has played an important role in tuning the second-order NLO response in this class of organic-inorganic hybrid compounds; particularly system 6 [Mo6O18(NC16H8F2(CF3)2I)]2–with the static second-order polarizability (βvec) computed to be 490.10 × 10-30esu. Thus, our studied systems have the feasibility to be excellent tuneable second-order NLO materials. The analysis of the major contributions to the βvecvalue suggests that the charge transfer (CT) from POM to organic ligand (D-A) along the z-axis has been enhanced with addition of F atoms at the end phenyl ring which directs head (POM) to tail (fluorinated ring) charge transfer. The computed βvecvalues have been tuned by incorporation of different halogen atoms at the end phenyl ring of organoimido segment. Furthermore, substitution of two trifluoromethyl (–CF3) groups sideways along with iodine (I) at the terminus of end phenyl ring in the organoimido ligand has a striking influence on tuning the optical non-linearity, as CT from POM to the organoimido ligand was significantly increased. These systematic small changes in molecular composition by substitution of different halogen groups leads to a tuning the NLO response; the so-called ‘ripple effect' catches this point nicely. Thus, the present investigation provides thought provoking insight into the tuneable NLO properties of organoimido-substituted hexamolybdates. [ABSTRACT FROM AUTHOR]

The emergence of biological phosphate esters of glycerol could have been a crucial step in the origin and evolution of life on the early Earth as glycerol phosphates today play a central role in biochemistry. We investigate here the formation of the glycerol phosphates by employing various rock samples, salts, and minerals as potential catalysts to aid the phosphorylation process. We report the synthesis of various phosphate esters of glycerol including glycerol-1-phosphate, glycerol-2-phosphate, cyclic glycerol-monophosphate as well as various diphosphate esters. Furthermore, the decomposition rates of glycerol phosphate under mild heating were also studied while keeping the pH constant. It was observed that glycerol phosphate starts decomposing quickly under mild heating conditions into inorganic orthophosphate and pyrophosphate, and a steady state concentration of ~0.5 M of glycerol phosphate may have been reasonable in ponds with abundant glycerol, phosphate, urea, and catalytic minerals. [ABSTRACT FROM AUTHOR]

The emergence and evolution of prebiotic biomolecules on the early Earth remain a question that is considered crucial to understanding the chemistry of the origin of life. Amongst prebiotic molecules, glycerol is significant due to its ubiquity in biochemistry. In this review, we discuss the significance of glycerol and its various derivatives in biochemistry, their plausible roles in the origin and evolution of early cell membranes, and significance in the biochemistry of extremophiles, followed by their prebiotic origin on the early Earth and associated catalytic processes that led to the origin of these compounds. We also discuss various scenarios for the prebiotic syntheses of glycerol and its derivates and evaluate these to determine their relevance to early Earth biochemistry and geochemistry, and recapitulate the utilization of various minerals (including clays), condensation agents, and solvents that could have led to the successful prebiotic genesis of these biomolecules. Furthermore, important prebiotic events such as meteoritic delivery and prebiotic synthesis reactions under astrophysical conditions are also discussed. Finally, we have also highlighted some novel features of glycerol, including glycerol nucleic acid (GNA), in the origin and evolution of the life. [ABSTRACT FROM AUTHOR]

The 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 31P-NMR. In addition to the above-mentioned products, a dimer of uridine-phosphate-uridine (U-P-U) was also observed. The reactions were promoted by white quartz sand, Mg2+, and by using urea as a condensation agent. The reactions also proceeded without this mixture; however, the yields increased remarkably with the presence of the above-mentioned materials. The results suggest that a hot/evaporating-drying pool of water containing organics, salts, and reactive phosphorus could be sufficient to form significant phosphate esters. [ABSTRACT FROM AUTHOR]

The cover page of the journal "Angewandte Chemie" is presented.

Charles Darwin schwebte 1871 die spontane Bildung biologischer Moleküle “in warmen Tümpeln mit allen möglichen Ammoniak ‐ und Phosphatsalzen” vor. In der Zuschrift auf S. 13443 ff. untersuchen C. Menor ‐ Salván, N. V. Hud et al. die Möglichkeit dieses präbiotischen Szenarios. Wenn sie eine Lösung von Ammoniumformiat, Harnstoff und Epsomit (die gezeigten Magnesiumsulfatkristalle) erhitzten, bildete sich ein Eutektikum, das Phosphat aus unlöslichem Apatit freisetzte, was zur Phosphorylierung von Nucleosiden führte. [ABSTRACT FROM AUTHOR]

Phosphorylation of the nucleosides adenosine and uridine by the simple mixing and mild heating of aqueous solutions of the organic compounds with synthetic analogs of the meteoritic mineral schreibersite, (Fe,Ni)3P under slightly basic conditions (pH ~9) is reported. These results suggest a potential role for meteoritic phosphorus in the origin and development of early life. [ABSTRACT FROM AUTHOR]