The coincidence of the Late Heavy Bombardment (LHB) period and the emergence of terrestrial life about 4 billion years ago suggest that extraterrestrial impacts could contribute to the synthesis of the building blocks of the first life-giving molecules. We simulated the high-energy synthesis of nucleobases from formamide during the impact of an extraterrestrial body. A high-power laser has been used to induce the dielectric breakdown of the plasma produced by the impact. The results demonstrate that the initial dissociation of the formamide molecule could produce a large amount of highly reactive CN and NH radicals, which could further react with formamide to produce adenine, guanine, cytosine, and uracil. Based on GC-MS, high-resolution FTIR spectroscopic results, as well as theoretical calculations, we present a comprehensive mechanistic model, which accounts for all steps taking place in the studied impact chemistry. Our findings thus demonstrate that extraterrestrial impacts, which were one order of magnitude more abundant during the LHB period than before and after, could not only destroy the existing ancient life forms, but could also contribute to the creation of biogenic molecules.
The Miller-Urey experiments pioneered modern research on the molecular origins of life, but their actual relevance in this field was later questioned because the gas mixture used in their research is considered too reducing with respect to the most accepted hypotheses for the conditions on primordial Earth. In particular, the production of only amino acids has been taken as evidence of the limited relevance of the results. Here, we report an experimental work, combined with state-of-the-art computational methods, in which both electric discharge and laser-driven plasma impact simulations were carried out in a reducing atmosphere containing NH 3 + CO. We show that RNA nucleobases are synthesized in these experiments, strongly supporting the possibility of the emergence of biologically relevant molecules in a reducing atmosphere. The reconstructed synthetic pathways indicate that small radicals and formamide play a crucial role, in agreement with a number of recent experimental and theoretical results. The following explorations showed that a broad array of amino acids could be synthesized, but there was no evidence that all of the fundamental molecules of the RNA genetic code could be produced alongside others in this type of experiment (2-5). Additionally, the significant persistence of reducing atmospheres in a geological timescale has been seriously debated (6). Finally, many scientists have claimed that this experiment is not related to early-Earth conditions and does not provide fundamental building blocks (i.e., nucleobases) important for the evolution of early life possibly based on RNA (7-13). In 2001, Saladino, Di Mauro, and coworkers (14) proposed that the parent molecule for the one-pot synthesis of nucleobases is formamide (15-23). Their team, together with other authors, demonstrated the formation of (not only) fundamental nucleobases for the origin of RNA in experiments involving the heating of formamide in presence of manifold catalysts (17,(24)(25)(26), upon UV irradiation (27), proton (28) and heavy-particle radiation (29), exposition to shock waves (18), etc. Recently, Hörst et al. (30) also referred to a positive result on qualitative detection of RNA nucleobases and manifold amino acids from tholines created in a N 2 , CH 4 , CO mixture. Their experiment simulated the atmosphere of Titan upon electric discharge. Such experimental results as well as theoretical expectations (31) show that reduced, relatively reactive atmospheres are likely to be more efficient for the synthesis of biomolecules (32). However, it should be noted that several papers report also the formation of biomolecules under neutral (N 2 , CO 2 , H 2 O) conditions (33-35). In our study, we found an interconnection between the original ideas of the pioneering Miller-Urey studies devoted to prebiotic synthesis in a reducing atmosphere and recent results identifying the chemistry of formamide as a source for the synthesis of nucleobases. In addition to traditional hydrogen cyanide (HCN)-based or reducing atmosphere-based concept...
Recent results in prebiotic chemistry implicate hydrogen cyanide (HCN) as the source of carbon and nitrogen for the synthesis of nucleotide, amino acid and lipid building blocks. HCN can be produced during impact events by reprocessing of carbonaceous and nitrogenous materials from both the impactor and the atmosphere; it can also be produced from these materials by electrical discharge. Here we investigate the effect of high energy events on a range of starting mixtures representative of various atmosphere-impactor volatile combinations. Using continuously scanning time–resolved spectrometry, we have detected ·CN radical and excited CO as the initially most abundant products. Cyano radicals and excited carbon monoxide molecules in particular are reactive, energy-rich species, but are resilient owing to favourable Franck–Condon factors. The subsequent reactions of these first formed excited species lead to the production of ground-state prebiotic building blocks, principally HCN.
High-resolution FT-IR spectroscopy was used for the analysis of the products of formamide dissociation using a high-energy Asterix laser. In the experiment, the detected products of the formamide LIDB dissociation were hydrogen cyanide, ammonia, carbon monoxide, carbon dioxide, nitrous oxide, hydroxylamine, and methanol. The molecular dynamics of the process was simulated with the use of a chemical model. The chemistry shared by formamide and the products of its dissociation is discussed with the respect to the formation of biomolecules.
Time-resolved Fourier transform (FT) spectrometry was used to study the dynamics of radical reactions forming the HCN and HNC isomers in pulsed glow discharges through vapors of BrCN, acetonitrile (CH(3)CN), and formamide (HCONH(2)). Stable gaseous products of discharge chemistry were analyzed by selected ion flow tube mass spectrometry (SIFT-MS). Ratios of concentrations of the HNC/HCN isomers obtained using known transition dipole moments of rovibrational cold bands v(1) were found to be in the range 2.2-3%. A kinetic model was used to assess the roles the radical chemistry and ion chemistry play in the formation of these two isomers. Exclusion of the radical reactions from the model resulted in a value of the HNC/HCN ratio 2 orders of magnitude lower than the experimental results, thus confirming their dominant role. The major process responsible for the formation of the HNC isomer is the reaction of the HCN isomer with the H atoms. The rate constant determined using the kinetic model from the present data for this reaction is 1.13 (±0.2) × 10(-13) cm(3) s(-1).
Context. It is well known that hydrogen cyanide and formamide can universally be considered as key molecules in prebiotic synthesis. Despite the fact that formamide has been detected in interplanetary and interstellar environments, other prebiotic species are far more abundant, including, for example, formaldehyde. However, several results indicate that formamide can play the role of important intermediate as well as that of a feedstock molecule in chemical abiogenesis. Diverse recently proposed scenarios of the origins of the first biopolymers show that liquid formamide environments could have been crucial for the formation of nucleobases, nucleosides, and for phosphorylation reactions, which lead to nucleotides. Aims. Here we report on a wide exploration of the formaldehyde reaction network under plasma conditions mimicking an asteroid descent in an Earth-like atmosphere and its impact. Methods. Dielectric breakdown using a high-power kJ-class laser system (PALS – Prague Asterix Laser System) along with quantum mechanical, ab initio molecular dynamics, and enhanced sampling simulations have been employed in order to mimic an asteroid impact plasma. Results. Being more abundant than formamide both in interstellar and interplanetary environments, during the era of early and late heavy bombardment of Earth and other planets, formaldehyde might have been delivered on asteroids to young planets. In the presence of nitrogen-bearing species, this molecule has been reprocessed under plasma conditions mimicking the local environment of an impacting body. We show that plasma reprocessing of formaldehyde leads to the formation of several radical and molecular species along with formamide. Conclusion. All the canonical nucleobases, the simplest amino acid (i.e., glycine), and the sugar ribose, have been detected after treatment of formaldehyde and nitrogen gas with dielectric breakdown. Our results, supported by quantum mechanical and enhanced sampling simulations, show that formaldehyde – by producing inter alia formamide – may have had the role of starting substance in prebiotic synthesis.
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