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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. [ABSTRACT FROM AUTHOR]

The photoinduced isomerization of diaminomaleonitrile (DAMN) to diaminofumaronitrile (DAFN) was suggested to play a key role in the prebiotically plausible formation of purine nucleobases and nucleotides. In this work we analyze two competitive photoisomerization mechanisms on the basis of state-of-the-art quantum-chemical calculations. Even though it was suggested that this process might occur on the triplet potential-energy surface, our results indicate that the singlet reaction channel should not be disregarded either. In fact, the peaked topography of the S1/S0 conical intersection suggests that the deexcitation should most likely occur on a sub-picosecond timescale and the singlet photoisomerization mechanism might effectively compete even with a very efficient intersystem crossing. Such a scenario is further supported by the relatively small spin-orbit coupling of the S1 and T2 states in the Franck-Condon region, which does not indicate a very effective triplet bypass for this photoreaction. Therefore, we conclude that the triplet reaction channel in DAMN might not be as prominent as was previously thought. [ABSTRACT FROM AUTHOR]

Base pairs belonging to the cis Hoogsteen:sugar-edge (H:S) family play important structural roles in folded RNA molecules. Several of these are present in internal loops, where they are involved in interactions leading to planar dinucleotide platforms which stabilize higher order structures such as base triplets and quartets. We report results of analysis of 30 representative examples spanning 16 possible base pair combinations, with several of them showing multimodality of base pairing geometry. The geometries of 23 of these base pairs were modeled directly from coordinates extracted from RNA crystal structures. The other seven were predicted structures which were modeled on the basis of observed isosteric analogues. After appropriate satisfaction of residual valencies, these structures were relaxed using the B3LYP/6-31G(d,p) method and interaction energies were derived at the RIMP2/aug-cc-pVDZ level of theory. The geometries for each of the studied base pairs have been characterized in terms of the number and nature of H-bonds, rmsd values observed on optimization, base pair geometrical parameters, and sugar pucker analysis. In addition to its evaluation, the nature of intermolecular interaction in these complexes was also analyzed using Morokuma decomposition. The gas phase interaction energies range between −5.2 and −20.6 kcal/mol and, in contrast to the H:S trans base pairs, show enhanced relative importance of the electron correlation component, indicative of the greater role of dispersion energy in stabilization of these base pairs. The rich variety of hydrogen bonding pattern, involving the flexible sugar edge, appears to hold the key to several features of structural motifs, such as planarity and propensity to participate in triplets, observed in this family of base pairs. This work explores these aspects by integrating database analysis, and detailed base pairing geometry analysis at the atomistic level, with ab initio computation of interaction energies. The study, involving alternative classification of base pairs and triplets, provides insights into intrinsic properties of these base pairs and their possible structural and functional roles. [ABSTRACT FROM AUTHOR]

Chemical environments of young planets are assumed to be significantly influenced by impacts of bodies lingering after the dissolution of the protoplanetary disk. We explore the chemical consequences of impacts of these bodies under reducing planetary atmospheres dominated by carbon monoxide, methane, and molecular nitrogen. Impacts were simulated by using a terawatt high-power laser system. Our experimental results show that one-pot impact-plasma-initiated synthesis of all the RNA canonical nucleobases and the simplest amino acid glycine is possible in this type of atmosphere in the presence of montmorillonite. This one-pot synthesis begins with de novo formation of hydrogen cyanide (HCN) and proceeds through intermediates such as cyanoacetylene and urea. [ABSTRACT FROM AUTHOR]

The formation of nucleobases fromformamide during a high-energydensity event, i.e., the impact of an extraterrestrial body into theplanetary atmosphere, was studied by irradiation of formamide iceand liquid samples with a high-power laser in the presence of potentialcatalysts. FTIR spectroscopy, time-resolved emission spectroscopy,and GC-MS were subsequently used to monitor the dissociation of thismolecule into stable molecular fragments (HCN, H2O, HNCO,H2, CO, and NH3) and unstable species (HNC,•CN, and •NH). The kinetic and thermodynamic modelsof the high-energy density event molecular dynamics have been suggestedtogether with the reaction routes leading from the dissociation productsto the nucleobases. In addition, using theoretical calculations, wepropose a simple new reaction pathway for the formation of both pyrimidineand purine nucleobases involving •CN radical chemistry. [ABSTRACT FROM AUTHOR]