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In this work Titan’s atmospheric chemistry is simulated using a capacitively coupled plasma radio frequency discharge in a N2−CH4stationnary flux. Samples of Titan’s tholins are produced in gaseous mixtures containing either 2 or 10% methane before the plasma discharge, covering the methane concentration range measured in Titan’s atmosphere. We study their solubility and associated morphology, their infrared spectroscopy signature and the mass distribution of the soluble fraction by mass spectrometry. An important result is to highlight that the previous Titan’s tholin solubility studies are inappropriate to fully characterize such a heterogeneous organic matter and we develop a new protocol to evaluate quantitatively tholins solubility. We find that tholins contain up to 35% in mass of molecules soluble in methanol, attached to a hardly insoluble fraction. Methanol is then chosen as a discriminating solvent to characterize the differences between soluble and insoluble species constituting the bulk tholins. No significant morphological change of shape or surface feature is derived from scanning electron microscopy after the extraction of the soluble fraction. This observation suggests a solid structure despite an important porosity of the grains. Infrared spectroscopy is recorded for both fractions. The IR spectra of the bulk, soluble, and insoluble tholins fractions are found to be very similar and reveal identical chemical signatures of nitrogen bearing functions and aliphatic groups. This result confirms that the chemical information collected when analyzing only the soluble fraction provides a valuable insight representative of the bulk material. The soluble fraction is ionized with an atmospheric pressure photoionization source and analyzed by a hybrid mass spectrometer. The congested mass spectra with one peak at every mass unit between 50 and 800 u confirm that the soluble fraction contains a complex mixture of organic molecules. The broad distribution, however, exhibits a regular pattern of mass clusters. Tandem collision induced dissociation analysis is performed in the negative ion mode to retrieve structural information. It reveals that (i) the molecules are ended by methyl, amine and cyanide groups, (ii) a 27 u neutral moiety (most probably HCN) is often released in the fragmentation of tholin anions, and (iii) an ubiquitous ionic fragment at m/z66 is found in all tandem spectra. A tentative structure is proposed for this negative ion. [ABSTRACT FROM AUTHOR]

We use laboratory experiments to derive information on the chemistry occurring during the evolution of astrophysical ices from dense molecular clouds to interplanetary objects. Through a new strategy that consists of coupling very high resolution mass spectrometry and infrared spectroscopy (FT-IR), we investigate the molecular content of the organic residues synthesized from different initial ice compositions. We also obtain information on the evolution of the soluble part of the residues after their over-irradiation. The results give insight into the role of water ice as a trapping and diluting agent during the chemical evolution. They also give information about the importance of the amount of ammonia in such ices, particularly regarding its competition with the carbon chemistry. All of these results allow us to build a first mapping of the evolution of soluble organic matter based on its chemical and physical history. Furthermore, our results suggest that interstellar ices should lead to organic materials enriched in heteroatoms that present similarities with cometary materials but strongly differ from meteoritic organic material, especially in their C/N ratios. [ABSTRACT FROM AUTHOR]