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Thèse De Doctorat UNIVERSITÉ PARIS-SUD ÉCOLE DOCTORALE 127 : ASTRONOMIE ET ASTROPHYSIQUE D’ÎLE-DE-FRANCE Laboratoire : Institut d’Astrophysique Spatiale THÈSE DE DOCTORAT PHYSIQUE par Paola MODICA From astrophysics to astrobiology: Significance of laboratory organic residues from photo-irradiation of cosmic ice analogs Date de soutenance : 26/11/2014 Composition du jury : Directeur de thèse : Louis LE SERGEANT D’HENDECOURT Directeur de recherche (IAS – CNRS - Université Paris-Sud) Rapporteurs : Hervé COTTIN Professeur (LISA - Université Paris-Est) Murthy GUDIPATI Principal Scientist (JPL - California Institute of Technology) Examinateurs : Guillaume PINEAU DES FORETS Professeur (IAS - Université Paris-Sud) Matthieu GOUNELLE Professeur (IMPMC - MNHN) Fathi MOUSSA Professeur (LETIAM - Université Paris-Sud) Membre invité : Michel VISO Responsable du programme Exobiologie (CNES) Acknowledgments During my PhD I received help, advice, and support from many people to whom I would like to show my greatest gratitude. First of all I would like to express my special appreciation and thanks to my advisor Louis Le Sergeant d’Hendecourt for being such a remarkable mentor. His dynamism and confidence in obtained results were always encouraging me to perseverate. I would like to stress here his great spirit of sacrifice in accompanying me through this long scientific project until the day of my thesis defense and his constant concern in doing everything possible to make me feel at ease in my life in France, both emotionally and financially. As his last student, I hope having contributed to end in style his scientific mentoring activity. Then I would like to thank all the members of the jury for letting my defense be a pleasant moment. In particular, I would like to offer my very sincere gratitude to the kind reviewers Professor Hervé Cottin and Doctor Murthy Gudipati for the time they have spent reading the manuscript and writing such detailed reports that were rich in useful remarks and suggestions. I feel really honored that both of them appreciated my work and contributed with enthusiasm in the complementation of the manuscript. I would also like to extend my thanks and appreciation to Professor Guillaume Pineau des Forêts for accepting the role of the jury president, Doctor Michel Viso for participating as jury guest member, Professor Fathi Moussa and Professor Matthieu Gounelle for finding the time in their schedule. Most of the results in this thesis are the product of several collaborations. Therefore, it is a pleasure to extend my gratitude to Laurent Nahon and his staff at the DESIRS beamline of SOLEIL Synchrotron from whom I have greatly benefited during the course of two experimental campaigns. I am thankful to Uwe Meierhenrich for welcoming me several times in the ICN laboratory in Nice and for the useful discussions we had. I am extremely grateful to Cornelia Meinert for providing very accurate analysis of samples with GCxGC MS in the same laboratory and for her irreplaceable help on circular dichroism applications. I am really thankful to Zita Martins of Imperial College in London for sharing her expertise in meteorites and for performing GC MS analysis of the “Paris” meteorite and the organic residues. Furthermore, I am very grateful to Denis Lesage of UPMC in Paris for his precious guide in the FT ICR analysis of organic samples and for his genuine interest in my work. I am also thankful to Roland Thissen for his warm welcoming at IPAG in Grenoble and his constructive criticism on FT ICR data interpretation. Naturally, I wish to thank the entire “Astrochimie et Origines” team for all the help, useful advises, and suggestions. In particular, I acknowledge my gratitude to my colleague Sihane Merouane for the production of silicate analogs, Zahia Djouadi for her support in the experiments with silicates and for reading part of my manuscript, Emmanuel Dartois, Donia Baklouti, Rosario Brunetto who participated in many different occasions to the implementation of this thesis, Ivan Alata and Lisseth Gavilan for the really good time spent together talking about everything. I wish to thank the two engineers of the team, Obadias Mivumbi and Philippe Duret, for their admirable technical assistance, constant help and (last but not least) for providing an amusing and relaxed atmosphere at work. Undoubtedly, a very special mention goes to Pierre de Marcellus from whom I learned how to operate in the laboratory and whose thesis was my personal bible. He is a very caring person whose effectiveness and relaxed attitude was an exemplar to me. I am very grateful for his help in speeding my work and accurately reviewing my writing and, above all, I would like to heartily thank him for his invaluable support in the moments of frustration. Certainly, I wish to take this opportunity to thank my friends and colleagues. First, I would like to express my appreciation from the deepest of the heart to Manale Noun for her selfless support and sacrifice at times of critical need during my oral presentation preparation. She is the nicest person imaginable and I owe her my eternal gratitude. Many thanks also to all my PhD colleagues that contributed to make these years more enjoyable: Vincent, Agnes, Lapo, Anna, JB, Andrea, Marco, Antoine… Moreover, a big thank to my friends out of academia for always being a major source of support when the circumstances were somewhat discouraging: (in casual order) Bernard, Natalia, Vladimiro, Michele, Pierre, Antoine, Cinzia, Giannis, Dmitri, Cecilia, Magda, Simona, Mariella, François, Marc, Maxim, Zuzana, Damien, Toni, Andreas... Finally, I would like to thank my family for understanding and supporting me during these years far from home and for always showing how proud they are of me. From astrophysics to astrobiology: Significance of laboratory organic residues from photo-irradiation of cosmic ice analogs Abstract Laboratory experiments have shown that ultraviolet photo-irradiation of astrophysical ice analogs and their following warm-up until room temperature lead to the formation of refractory organic residues. These residues consist of rich mixtures of organic compounds, including amino acids, which have a potential importance for prebiotic chemistry. They are considered as analogs of the organic refractory materials that are thought to be synthesized on dust grains in molecular clouds and/or in protoplanetary disks, as a product of the ice evolution, and that could be later accreted into comets and asteroids and eventually be delivered to the early Earth. Hence, the study of these analogs, produced under astrophysically relevant conditions, represents a valid tool to investigate the processes at work for the origin of complex organic molecules in the Solar System and, in particular, the possible introduction of enantiomeric excesses in chiral molecules. This PhD work is devoted to the study of these laboratory organic residues, their characterization and the astrophysical applications of these results. We used different analytical techniques such as gas chromatography mass spectrometry (GC MS, classical and multidimensional), Fourier transform ion cyclotron resonance mass spectrometry (FT ICR MS), and infrared spectroscopy. We measured the enantiomeric excesses induced in five chiral amino acids by UV circularly polarized light (UV CPL) irradiation of our analogs and insert these results in a coherent astrophysical scenario for the origin of the enantiomeric excesses observed in meteoritic amino acids. We studied the amino acid content of the Paris meteorite and evidence some similarities with the distribution of the amino acids in our organic residues. We also produced more realistic analogs of interstellar grains, including a silicate surface, to test the potential effects of such a surface on the formation and nature of organic residues. Finally, we discuss the significance of these results in the astrophysical context and the possible relationship between astrochemistry and prebiotic chemistry. De l'astrophysique à l'astrobiologie : L'intérêt des résidus organiques de laboratoire issus de la photo-irradiation d'analogues de glaces cosmiques Résumé Les expériences de laboratoire ont montré que la photo-irradiation ultraviolette d'analogues de glaces astrophysiques suivie de leur réchauffement à température ambiante mène à la formation de résidus organiques réfractaires. Ces résidus, solubles dans l'eau, consistent en un riche mélange de composés organiques incluant entre autres des acides aminés, molécules potentiellement importantes pour la chimie prébiotique. Ces résidus sont considérés comme des analogues de la matière organique réfractaire que l'on pense être synthétisée sur les grains de poussière dans les nuages moléculaires et/ou dans les disques protoplanétaires, produit de l'évolution des glaces, et qui pourra être accrétée plus tard en comètes ou en astéroïdes et finalement délivrée sur la Terre primitive. Ainsi, l'étude de ces analogues, produits dans des conditions astrophysiques pertinentes, représente un outil efficace pour explorer les processus à l'origine de la formation des molécules organiques complexes dans le Système Solaire et en particulier la possible introduction d'excès énantiomériques dans les molécules chirales. Ce travail de thèse est consacré à l'étude de ces résidus organiques, leur caractérisation et les applications astrophysiques de ces résultats. Nous avons utilisé différentes techniques d'analyse comme la chromatographie en phase gazeuse couplée à la spectrométrie de masse (GC MS, classique
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