Identify low mass volatile organic compounds from cometary ice analogs using gas chromatography coupled to an Orbitrap mass spectrometer associated to electron and chemical ionizations.

Analysis of organic matter extracted from meteorites showed that solar system objects present an important molecular diversity. To improve our understanding of such organic matter, new analytical technologies must be developed. The present study displays the first experiments using a GC-FT-Orbitrap-MS to decipher the molecular diversity observed in experiments simulating the evolution of cometary ices. The proposed analytical strategy focuses on the analysis of 110 volatile organic compounds (VOC) with mainly 1 to 6 carbon atoms generated in such cometary ice analogs. Electron ionization (EI) and chemical ionization (CI) modes with methane (CH4) or ammonia (NH3) were optimized and compared. Those developments maximized the intensity of molecular, protonated or deprotonated ions, and improved high-resolution molecular formula unambiguous identification: EI mode is too energetic to provides there detection, while it is not the case in CI mode. Particularly, NH3 as a reagent gas improves amine identification in positive mode (PCI), and esters, alcohols, carbonyls, amides, carboxylic acids and nitriles in negative mode (NCI). The combination of both EI and CI mass spectrum analysis improves molecular identification, thanks to the detection of molecular, deprotonated or protonated ion of highest intensity and fragment formula assignments. The EI and NCI NH3 combination allows formula assignments up to 94% of our database with limit of detection up to 7 ppm. This procedure has been validated for untargeted GC-FT-Orbitrap-MS analysis of VOC coming from the processing of cometary ice analogs.

A Light-Releasable Potentially Prebiotic Nucleotide Activating Agent.

Investigations into the chemical origin of life have recently benefitted from a holistic approach in which possible atmospheric, organic, and inorganic systems chemistries are taken into consideration. In this way, we now report that a selective phosphate activating agent, namely methyl isocyanide, could plausibly have been produced from simple prebiotic feedstocks. We show that methyl isocyanide drives the conversion of nucleoside monophosphates to phosphorimidazolides under potentially prebiotic conditions and in excellent yields for the first time. Importantly, this chemistry allows for repeated reactivation cycles, a property long sought in nonenzymatic oligomerization studies. Further, as the isocyanide is released upon irradiation, the possibility of spatially and temporally controlled activation chemistry is thus raised.

Enantioresolution and quantification of monosaccharides by comprehensive two-dimensional gas chromatography.

This work presents the development of a simple and efficient analytical protocol for the direct enantioselective resolution of sugars. A racemic mixture of the C3 sugar d,l-glyceraldehyde and the C5 monosaccharides d,l-arabinose, d,l-ribose, d,l-xylose, and d,l-lyxose was subjected to derivatization with trifluoroacetic anhydride, and corresponding derivatives were separated on a ß-cyclodextrin column with excellent resolution factors. Even though each aldopentose shows beside the linear form four predominant cyclic hemiacetals being the α- and ß-furanose along with the α- and ß-pyranose, we show that the overall enantiomeric excess of each compound can be precisely determined. Moreover, the measured detection limit for derivatized aldopentoses ranges from 0.015 to 0.019pmol on the column, while the quantification limit varies from 0.5 to 0.64pmol on the column.