Carbon Atom Condensation on NH3-H2O Ices. An Alternative Pathway to Interstellar Methanimine and Methylamine.

The recent discovery of the nature and behavior of carbon atoms interacting with interstellar ices has prompted a number of investigations on the chemistry initiated by carbon accretion on icy interstellar dust. In this work, we expand the range of processes promoted by carbon accretion to the chemistry initiated by the interaction of this atom with ammonia (NH3) using quantum chemical calculations. We found that carbon addition to the ammonia molecule forms a rather stable radical, CNH3, that is easily hydrogenated. The complete hydrogenation network is later studied. Our calculations reveal that while conversion to simpler molecules like HCN and HNC is indeed a possible outcome promoted by H-abstraction reactions, methylamine is also easily formed (CH3NH2). In fact, the stability of methylamine against hydrogen abstraction makes this molecule the preferred product of the reaction network. Our results serve as a stepping stone toward the accurate modeling of C-addition reactions in realistic astrochemical kinetic models.

Computational Protocol for the Identification of Candidates for Radioastronomical Detection and Its Application to the C3H3NO Family of Isomers.

The C3H3NO family of isomers is relevant in astrochemistry, even though its members are still elusive in the interstellar medium. To identify the best candidate for astronomical detection within this family, we developed a new computational protocol based on the minimum-energy principle. This approach aims to identify the most stable isomer of the family and consists of three steps. The first step is an extensive investigation that characterizes the vast number of compounds having the C3H3NO chemical formula, employing density functional theory for this purpose. The second step is an energy refinement, which is used to select isomers and relies on coupled cluster theory. The last step is a structural improvement with a final energy refinement that provides improved energies and a large set of accurate spectroscopic parameters for all isomers lying within 30 kJ mol-1 above the most stable one. According to this protocol, vinylisocyanate is the most stable isomer, followed by oxazole, which is about 5 kJ mol-1 higher in energy. The other stable species are pyruvonitrile, cyanoacetaldehyde, and cyanovinylalcohol. For all of these species, new computed rotational and vibrational spectroscopic data are reported, which complement those already available in the literature or fill current gaps.

Spectroscopic Characterization of 3-Aminoisoxazole, a Prebiotic Precursor of Ribonucleotides.

The processes and reactions that led to the formation of the first biomolecules on Earth play a key role in the highly debated theme of the origin of life. Whether the first chemical building blocks were generated on Earth (endogenous synthesis) or brought from space (exogenous delivery) is still unanswered. The detection of complex organic molecules in the interstellar medium provides valuable support to the latter hypothesis. To gather more insight, here we provide the astronomers with accurate rotational frequencies to guide the interstellar search of 3-aminoisoxazole, which has been recently envisaged as a key reactive species in the scenario of the so-called RNA-world hypothesis. Relying on an accurate computational characterization, we were able to register and analyze the rotational spectrum of 3-aminoisoxazole in the 6-24 GHz and 80-320 GHz frequency ranges for the first time, exploiting a Fourier-transform microwave spectrometer and a frequency-modulated millimeter/sub-millimeter spectrometer, respectively. Due to the inversion motion of the -NH2 group, two states arise, and both of them were characterized, with more than 1300 lines being assigned. Although the fit statistics were affected by an evident Coriolis interaction, we were able to produce accurate line catalogs for astronomical observations of 3-aminoisoxazole.

Gas-phase identification of (Z)-1,2-ethenediol, a key prebiotic intermediate in the formose reaction.

Prebiotic sugars are thought to be formed on primitive Earth by the formose reaction. However, their formation is not fully understood and it is plausible that key intermediates could have formed in extraterrestrial environments and subsequently delivered on early Earth by cometary bodies. 1,2-Ethenediol, the enol form of glycolaldehyde, represents a highly reactive intermediate of the formose reaction and is likely detectable in the interstellar medium. Here, we report the identification and first characterization of (Z)-1,2-ethenediol by means of rotational spectroscopy. The title compound has been produced in the gas phase by flash vacuum pyrolysis of bis-exo-5-norbornene-2,3-diol at 750 °C, through a retro-Diels-Alder reaction. The spectral analysis was guided by high-level quantum-chemical calculations, which predicted spectroscopic parameters in very good agreement with the experiment. Our study provides accurate spectral data to be used for searches of (Z)-1,2-ethenediol in the interstellar space.

Ab Initio Study of Fine and Hyperfine Interactions in Triplet POH.

Phosphorous-containing molecules have a great relevance in prebiotic chemistry in view of the fact that phosphorous is a fundamental constituent of biomolecules, such as RNA, DNA, and ATP. Its biogenic importance has led astrochemists to investigate the possibility that P-bearing species could have formed in the interstellar medium (ISM) and subsequently been delivered to early Earth by rocky bodies. However, only two P-bearing molecules have been detected so far in the ISM, with the chemistry of interstellar phosphorous remaining poorly understood. Here, in order to shed further light on P-carriers in space, we report a theoretical spectroscopic characterisation of the rotational spectrum of POH in its 3A″ ground electronic state. State-of-the-art coupled-cluster schemes have been employed to derive rotational constants, centrifugal distortion terms, and most of the fine and hyperfine interaction parameters, while the electron spin-spin dipolar coupling has been investigated using the multi-configuration self-consistent-field method. The computed spectroscopic parameters have been used to simulate the appearance of triplet POH rotational and ro-vibrational spectra in different conditions, from cold to warm environments, either in gas-phase experiments or in molecular clouds. Finally, we point out that the predicted hyperfine structures represent a key pattern for the recognition of POH in laboratory and interstellar spectra.

Thiols in the ISM: first detection of HC(O)SH and confirmation of C2H5SH.

The chemical compounds carrying the thiol group (-SH) have been considered essential in recent prebiotic studies regarding the polymerization of amino acids. We have searched for this kind of compounds toward the Galactic Centre quiescent cloud G+0.693-0.027. We report the first detection in the interstellar space of the trans-isomer of monothioformic acid (t-HC(O)SH) with an abundance of ~ 1 × 10-10. Additionally, we provide a solid confirmation of the gauche isomer of ethyl mercaptan (g-C2H5SH) with an abundance of ~ 3 × 10-10, and we also detect methyl mercaptan (CH3SH) with an abundance of ~ 5 × 10-9. Abundance ratios were calculated for the three SH-bearing species and their OH-analogues, revealing similar trends between alcohols and thiols with increasing complexity. Possible chemical routes for the interstellar synthesis of t-HC(O)SH, CH3SH and C2H5SH are discussed, as well as the relevance of these compounds in the synthesis of prebiotic proteins in the primitive Earth.

Discovery in space of ethanolamine, the simplest phospholipid head group.

Cell membranes are a key element of life because they keep the genetic material and metabolic machinery together. All present cell membranes are made of phospholipids, yet the nature of the first membranes and the origin of phospholipids are still under debate. We report here the presence of ethanolamine in space, [Formula: see text]OH, which forms the hydrophilic head of the simplest and second-most-abundant phospholipid in membranes. The molecular column density of ethanolamine in interstellar space is N = (1.51[Formula: see text]0.07)[Formula: see text], implying a molecular abundance with respect to [Formula: see text] of [Formula: see text] Previous studies reported its presence in meteoritic material, but they suggested that it is synthesized in the meteorite itself by decomposition of amino acids. However, we find that the proportion of the molecule with respect to water in the interstellar medium is similar to the one found in the meteorite ([Formula: see text]). These results indicate that ethanolamine forms efficiently in space and, if delivered onto early Earth, could have contributed to the assembling and early evolution of primitive membranes.

Toward the RNA-World in the Interstellar Medium-Detection of Urea and Search of 2-Amino-oxazole and Simple Sugars.

In the past decade, astrochemistry has witnessed an impressive increase in the number of detections of complex organic molecules. Some of these species are of prebiotic interest such as glycolaldehyde, the simplest sugar, or aminoacetonitrile, a possible precursor of glycine. Recently, we have reported the detection of two new nitrogen-bearing complex organics, glycolonitrile and Z-cyanomethanimine, known to be intermediate species in the formation process of ribonucleotides within theories of a primordial RNA-world for the origin of life. In this study, we present deep and high-sensitivity observations toward two of the most chemically rich sources in the galaxy: a giant molecular cloud in the center of the Milky Way (G + 0.693-0.027) and a proto-Sun (IRAS16293-2422 B). Our aim is to explore whether the key precursors considered to drive the primordial RNA-world chemistry are also found in space. Our high-sensitivity observations reveal that urea is present in G + 0.693-0.027 with an abundance of ∼5 × 10-11. This is the first detection of this prebiotic species outside a star-forming region. Urea remains undetected toward the proto-Sun IRAS16293-2422 B (upper limit to its abundance of ≤2 × 10-11). Other precursors of the RNA-world chemical scheme such as glycolaldehyde or cyanamide are abundant in space, but key prebiotic species such as 2-amino-oxazole, glyceraldehyde, or dihydroxyacetone are not detected in either source. Future more sensitive observations targeting the brightest transitions of these species will be needed to disentangle whether these large prebiotic organics are certainly present in space.