Skip to main content Accessibility help

The non-destructive separation of diverse astrobiologically relevant organic molecules by customizable capillary zone electrophoresis and monolithic capillary electrochromatography

  • Kosuke Fujishima (a1) (a2), Szymon Dziomba (a3) (a4), Hajime Yano (a5), Seydina I. Kebe (a3), Mohamed Guerrouache (a3), Benjamin Carbonnier (a3) and Lynn J. Rothschild (a6)...


The in situ detection of organic molecules in space is key to understanding the variety and the distribution of the building blocks of life, and possibly the detection of extraterrestrial life itself. Gas chromatography mass spectrometry (GC-MS) has been the most sensitive analytical strategy for organic analyses in flight, and was used on missions from NASA's Viking, Phoenix, Curiosity missions to ESA's Rosetta space probe. While pyrolysis GC-MS revealed the first organics on Mars, this step alters or degrades certain fragile molecules that are excellent biosignatures including polypeptides, oligonucleotides and polysaccharides, rendering the intact precursors undetectable. We have identified a solution tailored to the detection of biopolymers and other biomarkers by the use of liquid-based capillary electrophoresis and electrochromatography. In this study, we show that a capillary electrochromatography approach using monolithic stationary phases with tailor-made surface chemistry can separate and identify various polycyclic aromatic hydrocarbons, nucleobases and aromatic acids that could be formed under astrophysically relevant conditions. In order to simulate flyby organic sample capture, we conducted hypervelocity impact experiments which consisted of accelerating peptide-soaked montmorillonite particles to a speed of 5.6 km s−1, and capturing them in an amorphous silica aerogel of 10 mg cm−3 bulk density. Bulk peptide extraction from aerogel followed by capillary zone electrophoresis led to the detection of only two stereoisomeric peptide peaks. The recovery rates of each step of the extraction procedure after the hypervelocity impact suggest that major peptide loss occurred during the impact. Our study provides initial exploration of feasibility of this approach for capturing intact peptides, and subsequently detecting candidate biomolecules during flight missions that would be missed by GC-MS alone. As the monolith-based electrochromatography technology could be customized to detect specific classes of compounds as well as miniaturized, these results demonstrate the potential of the instrumentation for future astrobiology-related spaceflight missions.


Corresponding author

Author for correspondence: Lynn J. Rothschild, E-mail: and Benjamin Carbonnier, E-mail:


Hide All

Contributed equally.



Hide All
Akbay, C, Shamsi, SA and Warner, IM (1997) Phosphated surfactants as pseudostationary phase for micellar electrokinetic chromatography: separation of polycyclic aromatic hydrocarbons. Electrophoresis 18, 253259.
Ali, I, Al-Othman, ZA, Al-Warthan, A, Asnin, L and Chudinov, A (2014) Advances in chiral separations of small peptides by capillary electrophoresis and chromatography. Journal of Separation Science 37, 24472466.
Alpert, AJ (1990) Hydrophilic-interaction chromatography for the separation of peptides, nucleic acids and other polar compounds. Journal of Chromatography 499, 177196.
Aubrey, AD, Chalmers, JH, Bada, JL, Grunthaner, FJ, Amashukeli, X, Willis, P, Skelley, AM, Mathies, RA, Quinn, RC, Zent, AP, Ehrenfreund, P, Amundson, R, Glavin, DP, Botta, O, Barron, L, Blaney, DL, Clark, BC, Coleman, M, Hofmann, BA, Josset, JL, Rettberg, P, Ride, S, Robert, F, Sephton, MA and Yen, A (2008) The Urey instrument: an advanced in situ organic and oxidant detector for Mars exploration. Astrobiology 8, 583595.
Barrett, RA, Zolensky, ME, Horz, F, Lindstrom, DJ and Gibson, EK (1992) Suitability of silica aerogel as a capture medium for interplanetary dust. Proceedings, 22nd Lunar and Planetary Science 22, 203212.
Belloche, A, Muller, HSP, Menten, KM, Schilke, P and Comito, C (2013) Complex organic molecules in the interstellar medium: IRAM 30 m line survey of Sagittarius B2(N) and (M). Astronomy and Astrophysics 559(A47), 1187.
Brownlee, DE, Hörz, F, Hrubsh, L, McDonnell, JAM, Tsou, P and Williams, J (1994) Eureka! Aerogel capture of meteoroids in space. Abstracts, Lunar and Planetary Science Conference, 183184.
Brownlee, D, Tsou, P, Aléon, J, Alexander, CM, Araki, T, Bajt, S, Baratta, GA, Bastien, R, Bland, P, Bleuet, P, Borg, J, Bradley, JP, Brearley, A, Brenker, F, Brennan, S, Bridges, JC, Browning, ND, Brucato, JR, Bullock, E, Burchell, MJ, Busemann, H, Butterworth, A, Chaussidon, M, Cheuvront, A, Chi, M, Cintala, MJ, Clark, BC, Clemett, SJ, Cody, G, Colangeli, L, Cooper, G, Cordier, P, Daghlian, C, Dai, Z, D'Hendecourt, L, Djouadi, Z, Dominguez, G, Duxbury, T, Dworkin, JP, Ebel, DS, Economou, TE, Fakra, S, Fairey, SA, Fallon, S, Ferrini, G, Ferroir, T, Fleckenstein, H, Floss, C, Flynn, G, Franchi, IA, Fries, M, Gainsforth, Z, Gallien, JP, Genge, M, Gilles, MK, Gillet, P, Gilmour, J, Glavin, DP, Gounelle, M, Grady, MM, Graham, GA, Grant, PG, Green, SF, Grossemy, F, Grossman, L, Grossman, JN, Guan, Y, Hagiya, K, Harvey, R, Heck, P, Herzog, GF, Hoppe, P, Hörz, F, Huth, J, Hutcheon, ID, Ignatyev, K, Ishii, H, Ito, M, Jacob, D, Jacobsen, C, Jacobsen, S, Jones, S, Joswiak, D, Jurewicz, A, Kearsley, AT, Keller, LP, Khodja, H, Kilcoyne, AL, Kissel, J, Krot, A, Langenhorst, F, Lanzirotti, A, Le, L, Leshin, LA, Leitner, J, Lemelle, L, Leroux, H, Liu, MC, Luening, K, Lyon, I, Macpherson, G, Marcus, MA, Marhas, K, Marty, B, Matrajt, G, McKeegan, K, Meibom, A, Mennella, V, Messenger, K, Messenger, S, Mikouchi, T, Mostefaoui, S, Nakamura, T, Nakano, T, Newville, M, Nittler, LR, Ohnishi, I, Ohsumi, K, Okudaira, K, Papanastassiou, DA, Palma, R, Palumbo, ME, Pepin, RO, Perkins, D, Perronnet, M, Pianetta, P, Rao, W, Rietmeijer, FJ, Robert, F, Rost, D, Rotundi, A, Ryan, R, Sandford, SA, Schwandt, CS, See, TH, Schlutter, D, Sheffield-Parker, J, Simionovici, A, Simon, S, Sitnitsky, I, Snead, CJ, Spencer, MK, Stadermann, FJ, Steele, A, Stephan, T, Stroud, R, Susini, J, Sutton, SR, Suzuki, Y, Taheri, M, Taylor, S, Teslich, N, Tomeoka, K, Tomioka, N, Toppani, A, Trigo-Rodríguez, JM, Troadec, D, Tsuchiyama, A, Tuzzolino, AJ, Tyliszczak, T, Uesugi, K, Velbel, M, Vellenga, J, Vicenzi, E, Vincze, L, Warren, J, Weber, I, Weisberg, M, Westphal, AJ, Wirick, S, Wooden, D, Wopenka, B, Wozniakiewicz, P, Wright, I, Yabuta, H, Yano, H, Young, ED, Zare, RN, Zega, T, Ziegler, K, Zimmerman, L, Zinner, E and Zolensky, M (2006) Comet 81P/Wild 2 under a microscope. Science 314, 17111716.
Burchell, MJ, Thomson, R and Yano, H (1998) Capture of hypervelocity particles in aerogel: in ground laboratory and low earth orbit. Planetary and Space Science 47, 189204.
Burchell, MJ, Foster, NJ, Ormond Prout, J, Dupin, D and Armes, SP (2009) Extent of thermal ablation suffered by model organic microparticles during aerogel capture at hypervelocities. Meteoritics & Planetary Science 44, 14071419.
Burchell, MJ, Cole, MJ, Price, MC, Kearsley, AT and Nixon, A (2010) Glycine survival in hypervelocity impacts in the laboratory into aerogel and onto aluminium foil. Lunar and Planetary Science Conference 41, 1637.
Burchell, MJ, Bowden, SA, Cole, M, Price, MC and Parnell, J (2014) Survival of organic materials in hypervelocity impacts of ice on sand, ice, and water in the laboratory. Astrobiology 14, 473485.
Burgi, DS and Chien, RL (1991) Optimization in sample stacking for high-performance capillary electrophoresis. Analytical Chemistry 63, 20422047.
Callahan, MP, Smith, KE, Cleaves, HJ, Ruzicka, J, Stern, JC, Glavin, DP, House, CH and Dworkin, JP (2011) Carbonaceous meteorites contain a wide range of extraterrestrial nucleobases. Proceedings of the National Academy of Sciences of the United States of America 108, 1399513998.
Carbonnier, B, Guerrouache, M, Denoyel, R and Millot, MC (2007) CEC separation of aromatic compounds and proteins on hexylamine-functionalized N-acryloxysuccinimide monoliths. Journal of Separation Science 30, 30003010.
Chen, JH, Shi, Q, Wang, YL, Li, ZY and Wang, S (2015) Dereplication of known nucleobase and nucleoside compounds in natural product extracts by capillary electrophoresis-high resolution mass spectrometry. Molecules 20, 54235437.
Cooper, G and Rios, AC (2016) Enantiomer excesses of rare and common sugar derivatives in carbonaceous meteorites. Proceedings of the National Academy of Sciences of the United States of America 113, E3322E3331.
Cooper, G, Reed, C, Nguyen, D, Carter, M and Wang, Y (2011) Detection and formation scenario of citric acid, pyruvic acid, and other possible metabolism precursors in carbonaceous meteorites. Proceedings of the National Academy of Sciences of the United States of America 108, 1401514020.
Coussot, G, Moreau, T, Faye, C, Vigier, F, Baqué, M, Le Postollec, A, Incerti, S, Dobrijevic, M and Vandenabeele-Trambouze, O (2017) Biochip-based instruments development for space exploration: influence of the antibody immobilization process on the biochip resistance to freeze-drying, temperature shifts and cosmic radiations. International Journal of Astrobiology 16, 190199.
Creamer, JS, Mora, MF and Willis, PA (2017) Enhanced resolution of chiral amino acids with capillary electrophoresis for biosignature detection in extraterrestrial samples. Analytical Chemistry 89, 13291337.
Domínguez, G (2009) Time evolution and temperatures of hypervelocity impact-generated tracks in aerogel. Meteoritics & Planetary Science 44, 14311443.
Dziomba, S, Kowalski, P, Slominska, A and Baczek, T (2014) Field-amplified sample injection coupled with pseudo-isotachophoresis technique for sensitive determination of selected psychiatric drugs in human urine samples after dispersive liquid-liquid microextraction. Analytica Chimica Acta 811, 8893.
Ehrenfreund, P, Rasmussen, S, Cleaves, J and Chen, L (2006) Experimentally tracing the key steps in the origin of life: the aromatic world. Astrobiology 6, 490520.
Elsila, JE, Glavin, DP and Dworkin, JP (2009) Cometary glycine detected in samples returned by Stardust. Meteoritics & Planetary Science 44, 13231330.
Engel, MH and Macko, SA (1997) Isotopic evidence for extraterrestrial non-racemic amino acids in the Murchison meteorite. Nature 389, 265268.
Glavin, DP, Callahan, MP, Dworkin, JP and Elsila, JE (2010) The effects of parent body processes on amino acids in carbonaceous chondrites. Meteoritics & Planetary Science 45, 19481972.
Guerrouache, M, Carbonnier, B, Vidal-Madjar, C and Millot, MC (2007) In situ functionalization of N-acryloxysuccinimide-based monolith for reversed-phase electrochromatography. Journal of Chromatography A 1149, 368376.
Guerrouache, M, Millot, M-C and Carbonnier, B (2009) Functionalization of macroporous organic polymer monolith based on succinimide ester reactivity for chiral capillary chromatography: a cyclodextrin click approach. Macromolecular Rapid Communications 30, 109113.
Guerrouache, M, Millot, MC and Carbonnier, B (2011) Capillary columns for reversed-phase CEC prepared via surface functionalization of polymer monolith with aromatic selectors. Journal of Separation Science 34, 22712278.
Guo, S, Duan, JA, Qian, D, Wang, H, Tang, Y, Qian, Y, Wu, D, Su, S and Shang, E (2013) Hydrophilic interaction ultra-high performance liquid chromatography coupled with triple quadrupole mass spectrometry for determination of nucleotides, nucleosides and nucleobases in Ziziphus plants. Journal of Chromatography A 1301, 147155.
Hiller, DA and Strobel, SA (2011) The chemical versatility of RNA. Philosophical Transactions of the Royal Society of London B Biological Sciences 366, 29292935.
Hörz, F and Zolensky, ME (2000) Impact features and projectile residues in aerogel exposed on Mir. Icarus 147, 559579.
Hörz, F, Cintala, MJ, Zolensky, ME, Bernhard, RB, Davidson, WE, Haynes, G, See, TH, Tsou, P and Brownlee, DE (1998) Capture of hypervelocity particles with low-density aerogel. NASA Technical Memorandum 98, 159.
Hörz, F, Cintala, MJ, See, TH and Messenger, KN (2009) Penetration tracks in aerogel produced by Al2O3 spheres. Meteoritics & Planetary Science 44, 12431264.
Jung, SH and Choe, JC (2013) Mechanisms of prebiotic adenine synthesis from HCN by oligomerization in the gas phase. Astrobiology 13, 465475.
Kaiser, RI, Stockton, AM, Kim, YS, Jensen, EC and Mathies, RA (2013) On the formation of dipeptides in interstellar model ices. The Astrophysical Journal 765, 111.
Kasicka, V (1999) Capillary electrophoresis of peptides. Electrophoresis 20, 30843105.
Kasicka, V (2006) Recent developments in capillary electrophoresis and capillary electrochromatography of peptides. Electrophoresis 27, 142175.
Kim, J, Jensen, EC, Stockton, AM and Mathies, RA (2013) Universal microfluidic automaton for autonomous sample processing: application to the Mars organic analyzer. Analytical Chemistry 85, 76827688.
Kitazawa, Y, Fujiwara, A, Kadono, T, Imagawa, K, Okada, Y and Uematsu, K (1999) Hypervelocity impact experiments on aerogel dust collector. Journal of Geophysical Research: Planets 104, 2203522052.
Lerner, NR, Peterson, E and Chang, S (1993) The Strecker synthesis as a source of amino-acids in carbonaceous chondrites - deuterium retention during synthesis. Geochimica et Cosmochimica Acta 57, 47134723.
Marrubini, G, Mendoza, BE and Massolini, G (2010) Separation of purine and pyrimidine bases and nucleosides by hydrophilic interaction chromatography. Journal of Separation Science 33, 803816.
Mathies, RA, Razu, ME, Kim, J, Stockton, AM, Turin, P and Butterworth, A (2017) Feasibility of detecting bioorganic compounds in Enceladus plumes with the Enceladus organic analyzer. Astrobiology 17, 902912.
Mita, H, Yamagishi, A, Yano, H, Okudaira, K, Kobayashi, K, Yokobori, SI, Tabata, M, Kawai, H, Hashimoto, H and Wg, T (2009) TANPOPO: astrobiology exposure and micrometeoroid capture experiments on the KIBO, ISS. Origins of Life and Evolution of Biospheres 39, 371372.
Mora, MF, Stockton, AM and Willis, PA (2012) Microchip capillary electrophoresis instrumentation for in situ analysis in the search for extraterrestrial life. Electrophoresis 33, 26242638.
Mora, MF, Jones, SM, Creamer, J and Willis, PA (2018) Extraction of amino acids from aerogel for analysis by capillary electrophoresis. Implications for a mission concept to Enceladus’ Plume. Electrophoresis 39, 620625.
Mousis, O, Lunine, JI, Waite, JH, Magee, B, Lewis, WS, Mandt, KE, Marquer, D and Cordier, D (2009) Formation conditions of Enceladus and origin of its methane reservoir. The Astrophysical Journal. Letters 701, L39L42.
Nixon, A, Burchell, MJ, Price, MC, Kearsley, AT and Jones, S (2012) Aerogel tracks made by impacts of glycine: implications for formation of bulbous tracks in aerogel and the Stardust mission. Meteoritics & Planetary Science 47, 623633.
Okudaira, K, Noguchi, T, Nakamura, T, Sugita, S, Sekine, Y and Yano, H (2004) Evaluation of mineralogical alteration of micrometeoroid analog materials captured in aerogel. Advances in Space Research 34, 22992304.
Patel, BH, Percivalle, C, Ritson, DJ, Duffy, CD and Sutherland, JD (2015) Common origins of RNA, protein and lipid precursors in a cyanosulfidic protometabolism. Nature Chemistry 7, 301307.
Pizzarello, S (2006) The chemistry of life's origin: a carbonaceous meteorite perspective. Accounts of Chemical Research 39, 231237.
Poinot, P and Geffroy-Rodier, C (2015) Searching for organic compounds in the Universe. TrAC-Trends in Analytical Chemistry 65, 112.
Powner, MW, Gerland, B and Sutherland, JD (2009) Synthesis of activated pyrimidine ribonucleotides in prebiotically plausible conditions. Nature 459, 239242.
Quirino, JP and Terabe, S (2000) Sample stacking of cationic and anionic analytes in capillary electrophoresis. Journal of Chromatography A 902, 119135.
Rix, CS, Sims, MR and Cullen, DC (2011) Immunological detection of small organic molecules in the presence of perchlorates: relevance to the life marker chip and life detection on Mars. Astrobiology 11, 839846.
Sandford, SA, Aléon, J, Alexander, CM, Araki, T, Bajt, S, Baratta, GA, Borg, J, Bradley, JP, Brownlee, DE, Brucato, JR, Burchell, MJ, Busemann, H, Butterworth, A, Clemett, SJ, Cody, G, Colangeli, L, Cooper, G, D'Hendecourt, L, Djouadi, Z, Dworkin, JP, Ferrini, G, Fleckenstein, H, Flynn, GJ, Franchi, IA, Fries, M, Gilles, MK, Glavin, DP, Gounelle, M, Grossemy, F, Jacobsen, C, Keller, LP, Kilcoyne, AL, Leitner, J, Matrajt, G, Meibom, A, Mennella, V, Mostefaoui, S, Nittler, LR, Palumbo, ME, Papanastassiou, DA, Robert, F, Rotundi, A, Snead, CJ, Spencer, MK, Stadermann, FJ, Steele, A, Stephan, T, Tsou, P, Tyliszczak, T, Westphal, AJ, Wirick, S, Wopenka, B, Yabuta, H, Zare, RN and Zolensky, ME (2006) Organics captured from comet 81P/Wild 2 by the stardust spacecraft. Science 314, 17201724.
Schmitt-Kopplin, P, Gabelica, Z, Gougeon, RD, Fekete, A, Kanawati, B, Harir, M, Gebefuegi, I, Eckel, G and Hertkorn, N (2010) High molecular diversity of extraterrestrial organic matter in Murchison meteorite revealed 40 years after its fall. Proceedings of the National Academy of Sciences of the United States of America 107, 27632768.
Schneider, CA, Rasband, WS and Eliceiri, KW (2012) NIH image to ImageJ: 25 years of image analysis. Nature Methods 9, 671675.
Scriba, GKE (2006) Recent advances in peptide and peptidomimetic stereoisomer separations by capillary electromigration techniques. Electrophoresis 27, 222230.
Scriba, GKE (2009) Recent developments in peptide stereoisomer separations by capillary electromigration techniques. Electrophoresis 30, S222S228.
Sekine, Y, Takano, Y, Yano, H, Funase, R, Takai, K, Ishihara, M, Shibuya, T, Tachibana, S, Kuramoto, K, Yabuta, H, Kimura, J and Furukawa, Y (2014) Exploration of Enceladus’ water-rich plumes toward understanding of chemistry and biology of the interior ocean. Aerospace Technology Japan 12, Tk_7Tk_11.
Sephton, MA and Botta, O (2008) Extraterrestrial organic matter and the detection of life. Space Science Reviews 135, 2535.
Spencer, MK, Clemett, SJ, Sandford, SA, Mckay, DS and Zare, RN (2009) Organic compound alteration during hypervelocity collection of carbonaceous materials in aerogel. Meteoritics & Planetary Science 44, 1524.
Stockton, AM, Chiesl, TN, Scherer, JR and Mathies, RA (2009) Polycyclic aromatic hydrocarbon analysis with the Mars organic analyzer microchip capillary electrophoresis system. Analytical Chemistry 81, 790796.
Sugahara, H and Mimura, K (2015) Peptide synthesis triggered by comet impacts: a possible method for peptide delivery to the early Earth and icy satellites. Icarus 257, 103112.
Summons, RE, Albrecht, P, McDonald, G and Moldowan, JM (2007) Molecular biosignatures. Space Science Reviews 135, 133159.
Tabata, M, Yano, H, Kawai, H, Imai, E, Kawaguchi, Y, Hashimoto, H and Yamagishi, A (2015) Silica aerogel for capturing intact interplanetary dust particles for the Tanpopo experiment. Origins of Life and Evolution Biospheres 45, 225229.
Tielens, AGGM (2008) Interstellar polycyclic aromatic hydrocarbon molecules. Annual Review of Astronomy and Astrophysics 46, 289337.
Tsou, P, Brownlee, DE, Sandford, SA, Hörz, F and Zolensky, ME (2003) Wild 2 and interstellar sample collection and Earth return. Journal of Geophysical Research: Planets 108(E10).
Westphal, AJ, Snead, C, Borg, J, Quirico, E, Raynal, PI, Zolensky, ME, Ferrini, G, Colangeli, L and Palumbo, P (2002) Small hypervelocity particles captured in aerogel collectors: location, extraction, handling and storage. Meteoritics & Planetary Science 37, 855865.
Westphal, AJ, Snead, C, Butterworth, A, Graham, GA, Bradley, JP, Bajt, S, Grant, PG, Bench, G, Brennan, S and Pianetta, P (2004) Aerogel keystones: extraction of complete hypervelocity impact events from aerogel collectors. Meteoritics & Planetary Science 39, 13751386.
Willis, PA, Creamer, JS and Mora, MF (2015) Implementation of microchip electrophoresis instrumentation for future spaceflight missions. Analytical and Bioanalytical Chemistry 407, 69396963.
Yabuta, H, Williams, LB, Cody, GD, Alexander, CMO and Pizzarello, S (2007) The insoluble carbonaceous material of CM chondrites: a possible source of discrete organic compounds under hydrothermal conditions. Meteoritics & Planetary Science 42, 3748.
Yano, H, Yamagishi, A, Hashimoto, H, Yokobori, S, Kebukawa, Y, Kawaguchi, Y, Kobayashi, K, Yabuta, H, Tabata, M and Higashide, M (2015) Tanpopo: a New micrometeoroid capture and astrobiology exposure in Leo: its first year operation and post-flight plan. 78th Annual Meeting of the Meteoritical Society 1856, 5395.
Zhang, CX and Thormann, W (1996) Head-column field-amplified sample stacking in binary system capillary electrophoresis: a robust approach providing over 1000-fold sensitivity enhancement. Analytical Chemistry 68, 25232532.



Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed