Organic Molecules in the Interstellar Medium

Nitriles play a key role as molecular precursors in prebiotic experiments based on the RNA-world scenario for the origin of life. These chemical compounds could have been partially delivered to the young Earth from extraterrestrial objects, stressing the importance of establishing the reservoir of nitriles in the interstellar medium. We report here the detection towards the molecular cloud G+0.693−0.027 of several nitriles, including cyanic acid (HOCN), and three C4H3N isomers (cyanoallene, CH2CCHCN; propargyl cyanide, HCCCH2CN; and cyanopropyne (CH3CCCN), and the tentative detections of cyanoformaldehyde (HCOCN), and glycolonitrile (HOCH2CN). We have also performed the first interstellar search of cyanoacetaldehyde (HCOCH2CN), which was not detected. Based on the derived molecular abundances of the different nitriles in G+0.693−0.027 and other interstellar sources, we have discussed their formation mechanisms in the ISM. We propose that the observed HOCN abundance in G+0.693−0.027 is mainly due to surface chemistry and subsequent shock-induced desorption, while HCOCN might be mainly formed through gas-phase chemistry. In the case of HOCH2CN, several grain-surface routes from abundant precursors could produce it. The derived abundances of the three C4H3N isomers in G+0.693−0.027 are very similar, and also similar to those previously reported in the dark cold cloud TMC-1. This suggests that the three isomers are likely formed through gas-phase chemistry from common precursors, possibly unsaturated hydrocarbons (CH3CCH and CH2CCH2) that react with the cyanide radical (CN). The rich nitrile feedstock found towards G+0.693−0.027 confirms that interstellar chemistry is able to synthesize in space molecular species that could drive the prebiotic chemistry of the RNA-world.

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Molecular Precursors of the RNA-World in Space: New Nitriles in the G+0.693−0.027 Molecular Cloud

During summer 2014, three hypersaline brines were discovered in two frozen lakes of Boulder Clay (Northern Victoria Valley, Antarctica). Ongoing research seeks to gain novel insights on the microbial ecology of such environments, in order to further the understanding of life adaptation to extreme conditions. To this aim, the abundance of prokaryotic cells (including cell morphologies and size for biomass conversion), the amount of viable cells (in terms of membrane-intact cells and respiring cells), the viral count, the physiological profiles at community level and the main microbial enzymatic activities were described. The brines differed each other in terms of prokaryotic cells’ abundance, size, and viability as well as viral abundance. Cell morphotypes and metabolic responses also varied among the brine samples. Underground interconnections were likely to occur, with the microbial community becoming more abundant and structured to better exploit the limited resource availability. Overall, complex interactions among multiple environmental factors, including marine water origin, depth horizon, isolation time of the brines, and climatic variations, reflected on the microbial community distribution patterns and highlighted the need to preserve these niches of extreme life.

The prokaryotic community in an extreme Antarctic environment: the brines of Boulder Clay lakes (Northern Victoria Land)

At the focus of abiotic chemical reactions is the synthesis of ribose. No satisfactory explanation was provided as to the missing link between the prebiotic synthesis of ribose and prebiotic RNA (preRNA). Hydrogen cyanide (HCN) is assumed to have been the principal precursor in the prebiotic formation of aldopentoses in the formose reaction and in the synthesis of ribose. Ribose as the best fitting aldopentose became the exclusive sugar component of RNA. The elevated yield of ribose synthesis at higher temperatures and its protection from decomposition could have driven the polymerization of the ribose-phosphate backbone and the coupling of nucleobases to the backbone. RNA could have come into being without the involvement of nucleotide precursors. The first nucleoside monophosphate is likely to have appeared upon the hydrolysis of preRNA contributed by the presence of reactive 2'-OH moieties in the preRNA chain. As a result of phosphorylation, nucleoside monophosphates became nucleoside triphosphates, substrates for the selective synthesis of genRNA.

Prebiotic Pathway from Ribose to RNA Formation

On the Origin of Sugar Handedness: Facts, Hypotheses and Missing Links-A Review

Over 200 molecules have been detected in multiple extraterrestrial environments, including glycolaldehyde (C2(H2O)2, GLA), a two-carbon sugar precursor that has been detected in regions of the interstellar medium. Its recent in situ detection on the nucleus of comet 67P/Churyumov-Gerasimenko and through remote observations in the comae of others provides tantalizing evidence that it is common on most (if not all) comets. Impact experiments conducted at the Experimental Impact Laboratory at NASA's Johnson Space Center have shown that samples of GLA and GLA mixed with montmorillonite clays can survive impact delivery in the pressure range of 4.5 to 25 GPa. Extrapolated to amounts of GLA observed on individual comets and assuming a monotonic impact rate in the first billion years of Solar System history, these experimental results show that up to 1023 kg of cometary GLA could have survived impact delivery, with substantial amounts of threose, erythrose, glycolic acid, and ethylene glycol also produced or delivered. Importantly, independent of the profile of the impact flux in the early Solar System, comet delivery of GLA would have provided (and may continue to provide) a reservoir of starting material for the formose reaction (to form ribose) and the Strecker reaction (to form amino acids). Thus, comets may have been important delivery vehicles for starting molecules necessary for life as we know it.

/pdf/cometary-glycolaldehyde-as-a-source-of-pre-rna-molecules-1y1q0f3s7c.pdf

Cometary Glycolaldehyde as a Source of pre-RNA Molecules.

Substituent effects in dioxovanadium(V) schiff-base complexes: Tuning the outcomes of oxidation reactions

Over 200 molecules have been detected in multiple extraterrestrial environments, including glycolaldehyde (C2(H2O)2, GLA), a two-carbon sugar precursor that has been detected in regions of the interstellar medium. Its recent in situ detection on the nucleus of comet 67P/Churyumov-Gerasimenko and via remote observations in the comae of others, provides tantalizing evidence that it is common on most (if not all) comets. Impact experiments conducted at the Experimental Impact Laboratory at NASA's Johnson Space Center have shown that samples of GLA and GLA mixed with montmorillonite clays can survive impact delivery in the pressure range of 4.5 GPa to 25 GPa. Extrapolated to amounts of GLA observed on individual comets and assuming a monotonic impact rate in the first billion years of solar system history, these experimental results show that up to 10^23 kg of cometary GLA could have survived impact delivery, with substantial amounts of threose, erythrose, glycolic acid, and ethylene glycol also produced or delivered. Importantly, independent of the profile of the impact flux in the early solar system, comet delivery of GLA would have provided (and may continue to provide) a reservoir of starting material for the formose reaction (to form ribose) and the Strecker reaction (to form amino acids). Thus, comets may have been important delivery vehicles for starting molecules necessary for life as we know it.

Vanessa P. McCaffrey

Papers

Cometary Glycolaldehyde as a Source of pre-RNA Molecules.

Substituent effects in dioxovanadium(V) schiff-base complexes: Tuning the outcomes of oxidation reactions

Cometary glycolaldehyde as a source of pre-RNA molecules