Synthesis Of Prebiotic Molecules Research Articles

Synthesis of Nucleic Acid Bases by Metal Ferrite Nanoparticles from a Single Carbon Atom Precursor Molecule: Formamide.

The synthesis of prebiotic molecules from simple precursors is believed to be a crucial scheme in order to study the origin of life processes. The present study describes the one-pot synthesis of purine and pyrimidine nucleic acid bases in the presence of pre-biologically significant binary metal oxide nanoparticles, metal ferrites, namely NiFe2O4, CoFe2O4, CuFe2O4, ZnFe2O4 and MnFe2O4. The products identified are cytosine, isocytosine, 4(3H)-pyrimidinone, adenine, hypoxanthine and purine. The ability of isocytosine (a constitutional isomer of cytosine) to recognize cytosine and guanine through normal and reversed Watson-Crick pairing respectively, demonstrates an important storyline for the genesis of ancient nucleic acids. The relevance of other synthesized nucleic acid bases with respect to the origin of life is also discussed. The divalent metal ions in iron oxide make it an appropriate catalytic system because it demonstrates excellent catalytic performance for the nucleic acid bases synthesis with significantly high yield, as compared to pure iron oxide and some other minerals like silica, alumina, manganese oxides and double metal cyanide complexes.

Photochemistry vs. radiation chemistry of cosmic ice analogs

AbstractWhile gas-phase reactions and surface reactions on bare carbonaceous or siliceous dust grains contribute to cosmic chemistry, the energetic processing of cosmic ices via photochemistry and radiation chemistry is thought to be the dominant mechanism for the cosmic synthesis of prebiotic molecules. Because most previous laboratory astrochemical studies have used light sources that produce >10 eV photons and are, therefore, capable of ionizing cosmic ice analogs, discerning the role of photochemistry vs. radiation chemistry in astrochemistry is challenging. By using a source whose photon energy does not exceed 8 eV, we have studied ammonia and methanol cosmic ice reactions attributable solely to photochemistry. We compare these results to those obtained in the same ultrahigh vacuum chamber with 1 keV electrons which instead initiate radiation chemistry in cosmic ice analogs.

Catalytic conversion of methanol to larger organic molecules over crystalline forsterite: Laboratory study and astrophysical implications

Laboratory catalytic reactions of methanol over heated crystalline silicates (forsterite) lead to the formation of gas-phase olefinic and polycyclic aromatic hydrocarbon (PAH) molecules, and are of potential importance in astrophysical environments including hot molecular cores, protoplanetary disks and shocks. In our experiments the methanol reagent, together with intermediate and product gas-phase molecular species were detected using time-of-flight mass-spectrometry (TOF-MS). A solid deposited on the crystalline forsterite surface was examined subsequently using high-resolution transmission electron microscopy and thermal gravimetric techniques and found to comprise amorphous and graphitic carbon. The chemical players in this work – gas-phase methanol, crystalline silicates and PAHs, have been identified spectroscopically in a range of astrophysical environments including young and evolved stars, protoplanetary disks, comets, captured dust particles and meteorites. It is envisaged that reactions on bare dust grains as studied here both experimentally and theoretically through DFT calculations, can have implications for chemical transformations and conversions, in forming PAH molecules and potentially in the synthesis of prebiotic molecules.

Water near its Supercritical Point and at Alkaline pH for the Production of Ferric Oxides and Silicates in Anoxic Conditions. A New Hypothesis for the Synthesis of Minerals Observed in Banded Iron Formations and for the Related Geobiotropic Chemistry inside Fluid Inclusions

An alternative hypothesis for the origin of the banded iron formations and the synthesis of prebiotic molecules is presented here. I show the importance of considering water near its supercritical point and at alkaline pH. It is based on the chemical equation for the anoxic oxidation of ferrous iron into ferric iron at high-subcritical conditions of water and high pH, that I extract from E-pH diagrams drawn for corrosion purposes (Geophysical Research s Vol 15, EGU2013–22 Bassez 2013, Orig Life Evol Biosph 45(1):5-13, Bassez 2015, Procedia Earth Planet Sci 17, 492-495, Bassez 2017a, Orig Life Evol Biosph 47:453-480, Bassez 2017b). The sudden change in solubility of silica, SiO2, at the critical point of water is also considered. It is shown that under these temperatures and pressures, ferric oxides and ferric silicates can form in anoxic terrains. No FeII oxidation by UV light, neither by oxygen is needed to explain the minerals of the Banded Iron Formations. The intervention of any kind of microorganisms, either sulfate-reducing, or FeII-oxidizing or O2-producing, is not required. The chemical equation for the anoxic oxidation of ferrous iron is applied to the hydrolyses of fayalite, Fe2SiO4 and ferrosilite, FeSiO3. It is shown that the BIF minerals of the Hamersley Group, Western Australia, and the Transvaal Supergroup, South Africa, are those of fayalite and ferrosilite hydrolyses and carbonations. The dissolution of crustal fayalite and ferrosilite during water-rock interaction needs to occur at T&P just below the critical point of water and in a rising water which is undersaturated in SiO2. Minerals of BIFs which can then be ejected at the surface from venting arcs are ferric oxide hydroxides, hematite, FeIII-greenalite, siderite. The greenalite dehydrated product minnesotaite forms when rising water becomes supersaturated in SiO2, as also riebeckite and stilpnomelane. Long lengths of siderite without ferric oxides neither ferric silicates can occur since the exothermic siderite formation is not so much dependent in T&P. It is also shown that the H2 which is released during hydrolysis/oxidation of fayalite/ferrosilite can lead to components of life, such as macromolecules of amino acids which are synthesized from mixtures of (CO, N2, H2O) in Sabatier-Senderens/Fischer-Tropsch & Haber-Bosch reactions or microwave or gamma-ray excitation reactions. I propose that such geobiotropic synthesis may occur inside fluid inclusions of BIFs, in the silica chert, hematite, FeIII-greenalite or siderite. Therefore, the combination of high-subcritical conditions of water, high solubility of SiO2 at these T&P values, formation of CO also at these T&P, high pH and anoxic water, leads to the formation of ferric minerals and prebiotic molecules in the process of geobiotropy.

A highly reactive precursor in the iron\xa0sulfide system

Iron sulfur (Fe–S) phases have been implicated in the emergence of life on early Earth due to their catalytic role in the synthesis of prebiotic molecules. Similarly, Fe–S phases are currently of high interest in the development of green catalysts and energy storage. Here we report the synthesis and structure of a nanoparticulate phase (FeSnano) that is a necessary solid-phase precursor to the conventionally assumed initial precipitate in the iron sulfide system, mackinawite. The structure of FeSnano contains tetrahedral iron, which is compensated by monosulfide and polysulfide sulfur species. These together dramatically affect the stability and enhance the reactivity of FeSnano.

Influence of the UV Environment on the Synthesis of Prebiotic Molecules

Ultraviolet radiation is common to most planetary environments and could play a key role in the chemistry of molecules relevant to abiogenesis (prebiotic chemistry). In this work, we explore the impact of UV light on prebiotic chemistry that might occur in liquid water on the surface of a planet with an atmosphere. We consider effects including atmospheric absorption, attenuation by water, and stellar variability to constrain the UV input as a function of wavelength. We conclude that the UV environment would be characterized by broadband input, and wavelengths below 204 nm and 168 nm would be shielded out by atmospheric CO2 and water, respectively. We compare this broadband prebiotic UV input to the narrowband UV sources (e.g., mercury lamps) often used in laboratory studies of prebiotic chemistry and explore the implications for the conclusions drawn from these experiments. We consider as case studies the ribonucleotide synthesis pathway of Powner et al. (2009) and the sugar synthesis pathway of Ritson and Sutherland (2012). Irradiation by narrowband UV light from a mercury lamp formed an integral component of these studies; we quantitatively explore the impact of more realistic UV input on the conclusions that can be drawn from these experiments. Finally, we explore the constraints solar UV input places on the buildup of prebiotically important feedstock gasses like CH4 and HCN. Our results demonstrate the importance of characterizing the wavelength dependence (action spectra) of prebiotic synthesis pathways to determine how pathways derived under laboratory irradiation conditions will function under planetary prebiotic conditions.

On the Interaction of Methyl Azide (CH3N3) Ices with Ionizing Radiation: Formation of Methanimine (CH2NH), Hydrogen Cyanide (HCN), and Hydrogen Isocyanide (HNC)

Methyl azide (CH(3)N(3)) might be a potential precursor in the synthesis of prebiotic molecules via nonequilibrium reactions on interstellar ices initiated by energetic galactic cosmic rays (GCR) and photons. Here, we investigate the effects of energetic electrons as formed in the track of cosmic ray particles and 193 nm photons with solid methyl azide at 10 K and the inherent formation of methanimine (CH(2)NH), hydrogen cyanide (HCN), and hydrogen isocyanide (HNC). We present a systematic kinetic study and outline feasible reaction pathways to these molecules. These processes might be also important in solar system analogue ices.

The Fe-rich clay microsystems in basalt-komatiite lavas: importance of Fe-smectites for pre-biotic molecule catalysis during the Hadean eon.

During the Hadean to early Archean period (4.5-3.5 Ga), the surface of the Earth's crust was predominantly composed of basalt and komatiite lavas. The conditions imposed by the chemical composition of these rocks favoured the crystallization of Fe-Mg clays rather than that of Al-rich ones (montmorillonite). Fe-Mg clays were formed inside chemical microsystems through sea weathering or hydrothermal alteration, and for the most part, through post-magmatic processes. Indeed, at the end of the cooling stage, Fe-Mg clays precipitated directly from the residual liquid which concentrated in the voids remaining in the crystal framework of the mafic-ultramafic lavas. Nontronite-celadonite and chlorite-saponite covered all the solid surfaces (crystals, glass) and are associated with tiny pyroxene and apatite crystals forming the so-called "mesostasis". The mesostasis was scattered in the lava body as micro-settings tens of micrometres wide. Thus, every square metre of basalt or komatiite rocks was punctuated by myriads of clay-rich patches, each of them potentially behaving as a single chemical reactor which could concentrate the organics diluted in the ocean water. Considering the high catalytic potentiality of clays, and particularly those of the Fe-rich ones (electron exchangers), it is probable that large parts of the surface of the young Earth participated in the synthesis of prebiotic molecules during the Hadean to early Archean period through innumerable clay-rich micro-settings in the massive parts and the altered surfaces of komatiite and basaltic lavas. This leads us to suggest that Fe,Mg-clays should be preferred to Al-rich ones (montmorillonite) to conduct experiments for the synthesis and the polymerisation of prebiotic molecules.

A possible prebiotic synthesis of purine, adenine, cytosine, and 4(3H)-pyrimidinone from formamide: implications for the origin of life

The synthesis of prebiotic molecules is a major problem in chemical evolution as well as in any origin-of-life theory. We report here a plausible new prebiotic synthesis of naturally occurring purine and pyrimidine derivatives from formamide under catalytic conditions. In the presence of CaCO 3 and different inorganic oxides, namely silica, alumine, kaolin, and zeolite (Y type), neat formamide undergoes the formation of purine, adenine, cytosine, and 4(3H)-pyrimidinone, from acceptable to good yields. The role of catalysts showed to be not limited to the improvement of the yield but it is also relevant in providing a high selectivity in the products distribution.

Carbonaceous micrometeorites from Antarctica.

Over 100 000 large interplanetary dust particles in the 50-500 micrometers size range have been recovered in clean conditions from approximately 600 tons of Antarctic melt ice water as both unmelted and partially melted/dehydrated micrometeorites and cosmic spherules. Flux measurements in both the Greenland and Antarctica ice sheets indicate that the micrometeorites deliver to the Earth's surface approximately 2000x more extraterrestrial material than brought by meteorites. Mineralogical and chemical studies of Antarctic micrometeorites indicate that they are only related to the relatively rare CM and CR carbonaceous chondrite groups, being mostly chondritic carbonaceous objects composed of highly unequilibrated assemblages of anhydrous and hydrous minerals. However, there are also marked differences between these two families of solar system objects, including higher C/O ratios and a very marked depletion of chondrules in micrometeorite matter; hence, they are "chondrites-without-chondrules." Thus, the parent meteoroids of micrometeorites represent a dominant and new population of solar system objects, probably formed in the outer solar system and delivered to the inner solar system by the most appropriate vehicles, comets. One of the major purposes of this paper is to discuss applications of micrometeorite studies that have been previously presented to exobiologists but deal with the synthesis of prebiotic molecules on the early Earth, and more recently, with the early history of the solar system.

Carbonaceous micrometeorites and the origin of life.

Giant micrometeorites (sizes ranging from approximately 50 to 500 micrometers), such as those that were first recovered from clean pre-industrial Antarctic ices in December 1987, represent by far the dominant source of extraterrestrial carbonaceous material accreted by the Earth's surface, about 50,000 times the amount delivered by meteorites (sizes > or = a few cm). They correspond to large interplanetary dust particles that survived unexpectedly well their hypervelocity impact with the Earth's atmosphere, contrary to predictions of theoretical models of such impacts. They are related to relatively rare groups of carbonaceous chondrites (approximately 2% of the meteorite falls) and not to the most abundant meteorites (oridinary chondrites and differentiated micrometeorites). About 80% of them appear to be highly unequilibrated fine-grained assemblages of mineral grains, where an abundant carbonaceous component is closely associated on a scale of < or = 0.1 micron to both hydrous and anhydrous minerals, including potential catalysts. These observations suggest that micrometeorites could have functioned as individual microscopic chemical reactors to contribute to the synthesis of prebiotic molecules on the early Earth, about 4 billion years ago. The recent identification of some of their complex organics (amino acids and polycyclic aromatic hydrocarbons), and the observation that they behave as very efficient 'cosmochromatographs', further support this 'early carbonaceous micrometeorite' scenario. Future prospects include identifying the host phases (probably ferrihydrite) of their complex organics, evaluating their catalytic activity, and assessing whether synergetic interactions between micrometeorites and favorable zones of the early Earth (such as submarine hydrothermal vents) accelerated and/or modified such synthesis.

Synthesis of prebiotic molecules ? Role of some carbonyl compounds in prebiotic chemistry

Methyleneaminoacetonitrile(MAAN) resulting from the interaction of formaldehyde, ammonia and hydrogen cyanide on hydrolysis under mildly alkaline conditions gives a number of amino acids and peptides. Various aldehydes react with glycine to give corresponding hydroxyalkyl amino acids, which on reduction with formic acid are converted to reduced amino acids. Formaldehyde reacts with uracil to give 5-hydroxymethyl uracil which on reduction with formic acid yields thymine. Pyrrole formed by heating serine reacts with aldehydes to form porphyrins. Clays do not seem to influence most of these reactions, except the uracil-formaldehyde — formic acid reaction which results in enhanced yield of thymine.