ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Tholinomics—Chemical Analysis of Nitrogen-Rich Polymers

View Author Information
Laboratoire de Chimie Physique, UMR 8000, CNRS, Université Paris-Sud 11, 91405 Orsay cedex, France
Laboratoire Atmosphères, Milieux, Observations Spatiales, Université de Versailles Saint Quentin, UMR 8190, 91371 Verrières-le-Buisson cedex, France
Laboratoire de Planétologie de Grenoble, UMR 5109, CNRS, Université Joseph Fourrier 38041, Grenoble cedex 9, France
Centre de Recherche de Gif, Institut de Chimie des Substances Naturelles, CNRS, avenue de la Terrasse 91198, Gif-sur-Yvette cedex, France
* Author to whom correspondence should be addressed. E-mail: [email protected]
Cite this: Anal. Chem. 2010, 82, 4, 1371–1380
Publication Date (Web):January 26, 2010
Copyright © 2010 American Chemical Society

    Article Views





    Read OnlinePDF (5 MB)
    Supporting Info (1)»


    The polymeric composition of Titan’s tholins—laboratory analogues of Titan’s aerosols—is elucidated using high-resolution mass spectrometry. This complex organic matter is produced by plasma discharge in a gaseous nitrogen−methane mixture and analyzed with a hybrid linear trap/orbitrap mass-spectrometer. The highly structured mass spectra are treated with tools developed for petroleomics (Kendrick and van Krevelen diagrams), with original adaptations for nitrogen-rich compounds. Our goal is to find the best chemical basis set to describe the compositional space that these polymers occupy, to shed light onto the chemical structure of tholins. We succeeded in assigning the molecules identified in the mass spectra of tholins to a small number of regularly distributed X-(CH2)m(HCN)n families, where the balanced copolymer (m = n) is determined to play a central role. Within each family, the polymer lengths n and m present Poisson-type distributions. We also identify the smallest species of a subset of families as linear and cyclic amino nitrile compounds of great astrobiological interest: biguanide, guanidin, acetamidine, aminoacetonitrile, and methylimidazole.

    Supporting Information

    Jump To

    Two additional figures (Figures S-1 and S-2) are provided separately. (PDF) This material is available free of charge via the Internet at

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 63 publications.

    1. Cédric Wolters, Véronique Vuitton, François-Régis Orthous-Daunay, Laurène Flandinet, Chao He, Sarah E. Moran, Sarah M. Hörst. Molecular Screening with Liquid Chromatography Coupled to Ultra-High-Resolution Mass Spectrometry: Chromatographic Methods and Data Treatment for Application to Complex Organic Matter in Astrophysical Materials. ACS Earth and Space Chemistry 2023, 7 (9) , 1661-1674.
    2. Barbara Cunha de Miranda, Gustavo A. Garcia, François Gaie-Levrel, Ahmed Mahjoub, Thomas Gautier, Benjamin Fleury, Laurent Nahon, Pascal Pernot, and Nathalie Carrasco . Molecular Isomer Identification of Titan’s Tholins Organic Aerosols by Photoelectron/Photoion Coincidence Spectroscopy Coupled to VUV Synchrotron Radiation. The Journal of Physical Chemistry A 2016, 120 (33) , 6529-6540.
    3. Markus Meringer, H. James Cleaves, II, and Stephen J. Freeland . Beyond Terrestrial Biology: Charting the Chemical Universe of α-Amino Acid Structures. Journal of Chemical Information and Modeling 2013, 53 (11) , 2851-2862.
    4. Anyin Li, Fred P. M. Jjunju, R. Graham Cooks. Nucleophilic Addition of Nitrogen to Aryl Cations: Mimicking Titan Chemistry. Journal of the American Society for Mass Spectrometry 2013, 24 (11) , 1745-1754.
    5. Morgan L. Cable, Sarah M. Hörst, Robert Hodyss, Patricia M. Beauchamp, Mark A. Smith, and Peter A. Willis . Titan Tholins: Simulating Titan Organic Chemistry in the Cassini-Huygens Era. Chemical Reviews 2012, 112 (3) , 1882-1909.
    6. Feng Xian, Christopher L. Hendrickson, and Alan G. Marshall . High Resolution Mass Spectrometry. Analytical Chemistry 2012, 84 (2) , 708-719.
    7. Julien Maillard, Nathalie Carrasco, Christopher P. Rüger, Audrey Chatain, Isabelle Schmitz-Afonso, Chad R. Weisbrod, Laetitia Bailly, Emilie Petit, Thomas Gautier, Amy M. McKenna, Carlos Afonso. Humid Evolution of Haze in the Atmosphere of Super-Earths in the Habitable Zone. Astrobiology 2023, 23 (6) , 723-732.
    8. Audrey Chatain, Nathalie Carrasco, Ludovic Vettier, Olivier Guaitella. Interaction dust–plasma in Titan's ionosphere: Feedbacks on the gas phase composition. Icarus 2023, 396 , 115502.
    9. Luoth Chou, Paul Mahaffy, Melissa Trainer, Jennifer Eigenbrode, Ricardo Arevalo, William Brinckerhoff, Stephanie Getty, Natalie Grefenstette, Victoria Da Poian, G. Matthew Fricke, Christopher P. Kempes, Jeffrey Marlow, Barbara Sherwood Lollar, Heather Graham, Sarah Stewart Johnson. Planetary Mass Spectrometry for Agnostic Life Detection in the Solar System. Frontiers in Astronomy and Space Sciences 2021, 8
    10. Lora Jovanović, Thomas Gautier, Laurent Broch, Silvia Protopapa, Tanguy Bertrand, Pascal Rannou, Marie Fayolle, Eric Quirico, Luc Johann, Aotmane En Naciri, Nathalie Carrasco. Optical constants of Pluto aerosol analogues from UV to near-IR. Icarus 2021, 362 , 114398.
    11. Zoé Perrin, Nathalie Carrasco, Audrey Chatain, Lora Jovanovic, Ludovic Vettier, Nathalie Ruscassier, Guy Cernogora. An Atmospheric Origin for HCN-Derived Polymers on Titan. Processes 2021, 9 (6) , 965.
    12. Cédric Wolters, Laurène Flandinet, Chao He, Junko Isa, François‐Régis Orthous‐Daunay, Roland Thissen, Sarah Hörst, Véronique Vuitton. Enhancing data acquisition for the analysis of complex organic matter in direct‐infusion Orbitrap mass spectrometry using micro‐scans. Rapid Communications in Mass Spectrometry 2020, 34 (15)
    13. Lora Jovanović, Thomas Gautier, Véronique Vuitton, Cédric Wolters, Jérémy Bourgalais, Arnaud Buch, François-Régis Orthous-Daunay, Ludovic Vettier, Laurène Flandinet, Nathalie Carrasco. Chemical composition of Pluto aerosol analogues. Icarus 2020, 346 , 113774.
    14. A. Chatain, N. Carrasco, N. Ruscassier, T. Gautier, L. Vettier, O. Guaitella. Interaction dust – plasma in Titan's ionosphere: An experimental simulation of aerosols erosion. Icarus 2020, 345 , 113741.
    15. Laura Selliez, Julien Maillard, Barnabe Cherville, Thomas Gautier, Laurent Thirkell, Bertrand Gaubicher, Isabelle Schmitz‐Afonso, Carlos Afonso, Christelle Briois, Nathalie Carrasco. High‐resolution mass spectrometry for future space missions: Comparative analysis of complex organic matter with LAb‐CosmOrbitrap and laser desorption/ionization Fourier transform ion cyclotron resonance. Rapid Communications in Mass Spectrometry 2020, 34 (10)
    16. Julien Maillard, Sébastien Hupin, Nathalie Carrasco, Isabelle Schmitz-Afonso, Thomas Gautier, Carlos Afonso. Structural elucidation of soluble organic matter: Application to Titan's haze. Icarus 2020, 340 , 113627.
    17. David Dubois, Nathalie Carrasco, Lora Jovanovic, Ludovic Vettier, Thomas Gautier, Joseph Westlake. Positive ion chemistry in an N2-CH4 plasma discharge: Key precursors to the growth of Titan tholins. Icarus 2020, 338 , 113437.
    18. T. Gautier, G. Danger, O. Mousis, F. Duvernay, V. Vuitton, L. Flandinet, R. Thissen, F.-R. Orthous-Daunay, A. Ruf, T. Chiavassa, L. S. d'Hendecourt. Laboratory experiments to unveil the molecular reactivity occurring during the processing of ices in the protosolar nebula. Earth and Planetary Science Letters 2020, 531 , 116011.
    19. Jennifer L. Berry, Melissa S. Ugelow, Margaret A. Tolbert, Eleanor C. Browne. The Influence of Gas-phase Chemistry on Organic Haze Formation. The Astrophysical Journal 2019, 885 (1) , L6.
    20. L. Selliez, C. Briois, N. Carrasco, L. Thirkell, R. Thissen, M. Ito, F.-R. Orthous-Daunay, G. Chalumeau, F. Colin, H. Cottin, C. Engrand, L. Flandinet, N. Fray, B. Gaubicher, N. Grand, J.-P. Lebreton, A. Makarov, S. Ruocco, C. Szopa, V. Vuitton, P. Zapf. Identification of organic molecules with a laboratory prototype based on the Laser Ablation-CosmOrbitrap. Planetary and Space Science 2019, 170 , 42-51.
    21. François-Régis Orthous-Daunay, Roland Thissen, Véronique Vuitton. Measured mass to stoichoimetric formula through exhaustive search. Proceedings of the International Astronomical Union 2019, 15 (S350) , 193-199.
    22. David Dubois, Nathalie Carrasco, Marie Petrucciani, Ludovic Vettier, Sarah Tigrine, Pascal Pernot. In situ investigation of neutrals involved in the formation of Titan tholins. Icarus 2019, 317 , 182-196.
    23. Ricardo Arevalo, Laura Selliez, Christelle Briois, Nathalie Carrasco, Laurent Thirkell, Barnabé Cherville, Fabrice Colin, Bertrand Gaubicher, Benjamin Farcy, Xiang Li, Alexander Makarov. An Orbitrap‐based laser desorption/ablation mass spectrometer designed for spaceflight. Rapid Communications in Mass Spectrometry 2018, 32 (21) , 1875-1886.
    24. Julien Maillard, Nathalie Carrasco, Isabelle Schmitz-Afonso, Thomas Gautier, Carlos Afonso. Comparison of soluble and insoluble organic matter in analogues of Titan's aerosols. Earth and Planetary Science Letters 2018, 495 , 185-191.
    25. Helen E. Maynard-Casely, Morgan L. Cable, Michael J. Malaska, Tuan H. Vu, Mathieu Choukroun, Robert Hodyss. Prospects for mineralogy on Titan. American Mineralogist 2018, 103 (3) , 343-349.
    26. Bernhard Jost, Antoine Pommerol, Olivier Poch, Yann Brouet, Sonia Fornasier, Nathalie Carrasco, Cyril Szopa, Nicolas Thomas. Bidirectional reflectance of laboratory cometary analogues to interpret the spectrophotometric properties of the nucleus of comet 67P/Churyumov-Gerasimenko. Planetary and Space Science 2017, 148 , 1-11.
    27. Bernhard Jost, Antoine Pommerol, Olivier Poch, Zuriñe Yoldi, Sonia Fornasier, Pedro Henrique Hasselmann, Clément Feller, Nathalie Carrasco, Cyril Szopa, Nicolas Thomas. Bidirectional reflectance and VIS-NIR spectroscopy of cometary analogues under simulated space conditions. Planetary and Space Science 2017, 145 , 14-27.
    28. Zita Martins, Hervé Cottin, Julia Michelle Kotler, Nathalie Carrasco, Charles S. Cockell, Rosa de la Torre Noetzel, René Demets, Jean-Pierre de Vera, Louis d’Hendecourt, Pascale Ehrenfreund, Andreas Elsaesser, Bernard Foing, Silvano Onofri, Richard Quinn, Elke Rabbow, Petra Rettberg, Antonio J. Ricco, Klaus Slenzka, Fabien Stalport, Inge L. ten Kate, Jack J. W. A. van Loon, Frances Westall. Earth as a Tool for Astrobiology—A European Perspective. Space Science Reviews 2017, 209 (1-4) , 43-81.
    29. Thomas Gautier, Joshua A. Sebree, Xiang Li, Veronica T. Pinnick, Andrej Grubisic, Mark J. Loeffler, Stephanie A. Getty, Melissa G. Trainer, William B. Brinckerhoff. Influence of trace aromatics on the chemical growth mechanisms of Titan aerosol analogues. Planetary and Space Science 2017, 140 , 27-34.
    30. Y. Brouet, A. C. Levasseur-Regourd, P. Sabouroux, L. Neves, P. Encrenaz, O. Poch, A. Pommerol, N. Thomas, W. Kofman, A. Le Gall, V. Ciarletti, A. Hérique, A. Lethuillier, N. Carrasco, C. Szopa. A porosity gradient in 67P/C-G nucleus suggested from CONSERT and SESAME-PP results: an interpretation based on new laboratory permittivity measurements of porous icy analogues. Monthly Notices of the Royal Astronomical Society 2016, 462 (Suppl 1) , S89-S98.
    31. Marietta Morisson, Cyril Szopa, Nathalie Carrasco, Arnaud Buch, Thomas Gautier. Titan's organic aerosols: Molecular composition and structure of laboratory analogues inferred from pyrolysis gas chromatography mass spectrometry analysis. Icarus 2016, 277 , 442-454.
    32. Ahmed Mahjoub, Martin Schwell, Nathalie Carrasco, Yves Benilan, Guy Cernogora, Cyril Szopa, Marie-Claire Gazeau. Characterization of aromaticity in analogues of titan's atmospheric aerosols with two-step laser desorption ionization mass spectrometry. Planetary and Space Science 2016, 131 , 1-13.
    33. Christelle Briois, Roland Thissen, Laurent Thirkell, Kenzi Aradj, Abdel Bouabdellah, Amirouche Boukrara, Nathalie Carrasco, Gilles Chalumeau, Olivier Chapelon, Fabrice Colin, Patrice Coll, Hervé Cottin, Cécile Engrand, Noel Grand, Jean-Pierre Lebreton, François-Régis Orthous-Daunay, Cyril Pennanech, Cyril Szopa, Véronique Vuitton, Pascal Zapf, Alexander Makarov. Orbitrap mass analyser for in situ characterisation of planetary environments: Performance evaluation of a laboratory prototype. Planetary and Space Science 2016, 131 , 33-45.
    34. Thomas Gautier, Isabelle Schmitz-Afonso, David Touboul, Cyril Szopa, Arnaud Buch, Nathalie Carrasco. Development of HPLC-Orbitrap method for identification of N-bearing molecules in complex organic material relevant to planetary environments. Icarus 2016, 275 , 259-266.
    35. Nathalie Carrasco, François Jomard, Jackie Vigneron, Arnaud Etcheberry, Guy Cernogora. Laboratory analogues simulating Titan's atmospheric aerosols: Compared chemical compositions of grains and thin films. Planetary and Space Science 2016, 128 , 52-57.
    36. Árpád Somogyi, Roland Thissen, Francois-Régis Orthous-Daunay, Véronique Vuitton. The Role of Ultrahigh Resolution Fourier Transform Mass Spectrometry (FT-MS) in Astrobiology-Related Research: Analysis of Meteorites and Tholins. International Journal of Molecular Sciences 2016, 17 (4) , 439.
    37. Olivier Poch, Antoine Pommerol, Bernhard Jost, Nathalie Carrasco, Cyril Szopa, Nicolas Thomas. Sublimation of ice–tholins mixtures: A morphological and spectro-photometric study. Icarus 2016, 266 , 288-305.
    38. Olivier Poch, Antoine Pommerol, Bernhard Jost, Nathalie Carrasco, Cyril Szopa, Nicolas Thomas. Sublimation of water ice mixed with silicates and tholins: Evolution of surface texture and reflectance spectra, with implications for comets. Icarus 2016, 267 , 154-173.
    39. O. Pirali, V. Boudon. Synchrotron-based Fourier transform spectra of the ν 23 and ν 24 IR bands of hexamethylenetetramine C6N4H12. Journal of Molecular Spectroscopy 2015, 315 , 37-40.
    40. Jing He, Arnaud Buch, Nathalie Carrasco, Cyril Szopa. Thermal degradation of organics for pyrolysis in space: Titan’s atmospheric aerosol case study. Icarus 2015, 248 , 205-212.
    41. G Wattieaux, N Carrasco, M Henault, L Boufendi, G Cernogora. Transient phenomena during dust formation in a N 2 –CH 4 capacitively coupled plasma. Plasma Sources Science and Technology 2015, 24 (1) , 015028.
    42. José L. de la Fuente, Marta Ruiz-Bermejo, Delphine Nna-Mvondo, Robert D. Minard. Further progress into the thermal characterization of HCN polymers. Polymer Degradation and Stability 2014, 110 , 241-251.
    43. Chao He, Mark A. Smith. A comprehensive NMR structural study of Titan aerosol analogs: Implications for Titan’s atmospheric chemistry. Icarus 2014, 243 , 31-38.
    44. Thomas Gautier, Nathalie Carrasco, Isabelle Schmitz-Afonso, David Touboul, Cyril Szopa, Arnaud Buch, Pascal Pernot. Nitrogen incorporation in Titan's tholins inferred by high resolution orbitrap mass spectrometry and gas chromatography–mass spectrometry. Earth and Planetary Science Letters 2014, 404 , 33-42.
    45. Chao He, Mark A. Smith. Identification of nitrogenous organic species in Titan aerosols analogs: Implication for prebiotic chemistry on Titan and early Earth. Icarus 2014, 238 , 86-92.
    46. H. James Cleaves, Catherine Neish, Michael P. Callahan, Eric Parker, Facundo M. Fernández, Jason P. Dworkin. Amino acids generated from hydrated Titan tholins: Comparison with Miller–Urey electric discharge products. Icarus 2014, 237 , 182-189.
    47. V. Vuitton, O. Dutuit, M. A. Smith, N. Balucani. Chemistry of Titan's atmosphere. 2014, 224-284.
    48. O. Pirali, V. Boudon, N. Carrasco, E. Dartois. Rotationally resolved IR spectroscopy of hexamethylenetetramine (HMT) C 6 N 4 H 12. Astronomy & Astrophysics 2014, 561 , A109.
    49. G. Danger, F.-R. Orthous-Daunay, P. de Marcellus, P. Modica, V. Vuitton, F. Duvernay, L. Flandinet, L. Le Sergeant d’Hendecourt, R. Thissen, T. Chiavassa. Characterization of laboratory analogs of interstellar/cometary organic residues using very high resolution mass spectrometry. Geochimica et Cosmochimica Acta 2013, 118 , 184-201.
    50. Chao He, Mark A. Smith. Identification of nitrogenous organic species in Titan aerosols analogs: Nitrogen fixation routes in early atmospheres. Icarus 2013, 226 (1) , 33-40.
    51. Marta Ruiz-Bermejo, María-Paz Zorzano, Susana Osuna-Esteban. Simple Organics and Biomonomers Identified in HCN Polymers: An Overview. Life 2013, 3 (3) , 421-448.
    52. P. Coll, R. Navarro-González, C. Szopa, O. Poch, S.I. Ramírez, D. Coscia, F. Raulin, M. Cabane, A. Buch, G. Israël. Can laboratory tholins mimic the chemistry producing Titan's aerosols? A review in light of ACP experimental results. Planetary and Space Science 2013, 77 , 91-103.
    53. Nathalie Carrasco, Joseph Westlake, Pascal Pernot, Hunter Waite. Nitrogen in Titan’s Atmospheric Aerosol Factory. 2013, 145-154.
    54. S. Derenne, C. Coelho, C. Anquetil, C. Szopa, A.S. Rahman, P.F. McMillan, F. Corà, C.J. Pickard, E. Quirico, C. Bonhomme. New insights into the structure and chemistry of Titan’s tholins via 13C and 15N solid state nuclear magnetic resonance spectroscopy. Icarus 2012, 221 (2) , 844-853.
    55. A. Mahjoub, N. Carrasco, P.-R. Dahoo, T. Gautier, C. Szopa, G. Cernogora. Influence of methane concentration on the optical indices of Titan’s aerosols analogues. Icarus 2012, 221 (2) , 670-677.
    56. Thomas Gautier, Nathalie Carrasco, Ahmed Mahjoub, Sandrine Vinatier, Alexandre Giuliani, Cyril Szopa, Carrie M. Anderson, Jean-Jacques Correia, Paul Dumas, Guy Cernogora. Mid- and far-infrared absorption spectroscopy of Titan’s aerosols analogues. Icarus 2012, 221 (1) , 320-327.
    57. Nathalie Carrasco, Thomas Gautier, Et-touhami Es-sebbar, Pascal Pernot, Guy Cernogora. Volatile products controlling Titan’s tholins production. Icarus 2012, 219 (1) , 230-240.
    58. Árpád Somogyi, Mark A. Smith, Véronique Vuitton, Roland Thissen, István Komáromi. Chemical ionization in the atmosphere? A model study on negatively charged “exotic” ions generated from Titan's tholins by ultrahigh resolution MS and MS/MS. International Journal of Mass Spectrometry 2012, 316-318 , 157-163.
    59. D. Tziotis, N. Hertkorn, Ph. Schmitt-Kopplin. Kendrick-Analogous Network Visualisation of Ion Cyclotron Resonance Fourier Transform Mass Spectra: Improved Options for the Assignment of Elemental Compositions and the Classification of Organic Molecular Complexity. European Journal of Mass Spectrometry 2011, 17 (4) , 415-421.
    60. Thomas Gautier, Nathalie Carrasco, Arnaud Buch, Cyril Szopa, Ella Sciamma-O’Brien, Guy Cernogora. Nitrile gas chemistry in Titan’s atmosphere. Icarus 2011, 213 (2) , 625-635.
    61. Sylvain Plessis, Nathalie Carrasco, Pascal Pernot. Knowledge-based probabilistic representations of branching ratios in chemical networks: The case of dissociative recombinations. The Journal of Chemical Physics 2010, 133 (13)
    62. E. Sciamma-O’Brien, N. Carrasco, C. Szopa, A. Buch, G. Cernogora. Titan’s atmosphere: An optimal gas mixture for aerosol production?. Icarus 2010, 209 (2) , 704-714.
    63. Véronique Vuitton, Jean-Yves Bonnet, Maeliss Frisari, Roland Thissen, Eric Quirico, Odile Dutuit, Bernard Schmitt, Léna Le Roy, Nicolas Fray, Hervé Cottin, Ella Sciamma-O'Brien, Nathalie Carrasco, Cyril Szopa. Very high resolution mass spectrometry of HCN polymers and tholins. Faraday Discussions 2010, 147 , 495.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect