Abstract
Biopolymers like DNA and proteins are strongly selective towards the chirality of their monomer units. The use of homochiral monomers is regarded as essential for the construction and function of biopolymers; the emergence of the molecular asymmetry is therefore considered as a fundamental step in Chemical Evolution. This work focuses on physicochemical mechanisms for the origin of biomolecular asymmetry. Very recently two groups, one from Allamandola at NASA Ames and the other from our Inter-European team, demonstrated simultaneously the spontaneous photoformation of a variety of chiral amino acid structures under simulated interstellar conditions. Since both groups used unpolarized light for the photoreaction the obtained amino acids turned out racemic as expected. The obtained experimental data support the assumption that tiny ice grains can furthermore play host to important asymmetric reactions when irradiated by interstellar circularly polarized ultraviolet light. It is possible that such ice grains could have become incorporated into the early cloud that formed our Solar System and ended up on Earth, assisting life to start. Several lines of evidence suggest that some of the building blocks of life were delivered to the primitive Earth via (micro-) meteoroids and/or comets. These results suggest that asymmetric interstellar photochemistry may have played a significant part in supplying Earth with some of the enantioenriched organic materials needed to trigger life. The search for the origin of biomolecular homochirality leads to a strong interest in the fields of asymmetric photochemistry with special emphasis on absolute asymmetric synthesis. We outline here the theoretical background on asymmetric interstellar ice photochemistry, summarize recent concepts and advances in the field, and discuss briefly its implications. The obtained data are crucial for the design of the enantioselective COSAC GC-MS experiment onboard the ROSETTA spacecraft to a comet to be launched in the very near future.
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Bailey, J.: 1998, Circular Polarization in Star-Formation Regions: Implications for Biomolecular Homochirality, Science 281, 672–674.
Bailey, J.: 2001, Astronomical Sources of CPL and the Origin of Homochirality, Orig. Life Evol. Biosphere 31, 167.
Balavoine, G., Moradpour, A. and Kagan, H. B.: 1974, Preparation of Chiral Compounds with High Optical Purity by Irradiation with Circularly Polarized Light, a Model Reaction for the Prebiotic Generation of Optical Activity, J. Am. Chem. Soc. 96, 5152–5158.
Bernstein, M. P., Dworkin, J. P., Sandford, S. A., Cooper, G. W. and Allamandola, L. J.: 2002, Racemic Amino Acids from the Ultraviolet Photolysis of Interstellar Ice Analogues, Nature 416, 401–403.
Bernstein, W. J., Calvin, M. and Burchardt, O.: 1972, Absolute Asymmetric Synthesis. I. On the Mechanism of the Photochemical Synthesis of Nonracemic Helicenes with Circularly Polarized Light. Wavelength Dependence of the Optical Yield of Octahelicene, J. Am. Chem. Soc. 94, 494–497.
Bernstein, W. J., Calvin, M. and Burchardt, O.: 1973, Absolute Asymmetric Synthesis. III. Hindered Rotation about Aryl-Ethylene Bonds in the Excited States of Diaryl ethylenes. Structural Effects on the Asymmetric Synthesis of 2-and 4-Substituted Hexahelicenes, J. Am. Chem. Soc. 95, 528–532.
Boillot, B., Meierhenrich, U., Chabin, A., Jacquet, R., Alcaraz, C., Dutuit, O., Brack, A., Nahon, L. and Barbier, B.: 2000, Origine de l'asymétrie des molécules biologiques. Poster-Presentation, Journées Soleil Région Centre, Orléans, France, 18–20 December 2000.
Bonner, W. A.: 1991, The Origin and Amplification of Biomolecular Chirality, Orig. Life Evol. Biosphere 21, 59–111.
Cerf, C. and Jorissen, A.: 2000, Is Amino-Acid Homochirality Due to Asymmetric Photolysis in Space? Space Sci. Rev. 92, 603–612.
Cronin, J. R. and Pizzarello, S.: 1997, Enantiomeric Excesses in Meteoritic Amino Acids, Science 275, 951–955.
Engel, M. H. and Macko, S. A.: 1997, Isotopic Evidence for Extraterrestrial Non-Racemic Amino Acids in the Murchison Meteorite, Nature 389, 265–268.
Flores, J. J., Bonner, W. A. and Massey, G. A.: 1977, Asymmetric Photolysis of (RS)-Leucine with Circularly Polarized Ultraviolet Light, J. Am. Chem. Soc. 99, 3622–3625.
Greenberg, J. M.: 1993, Physical and Chemical Composition of Comets — from Interstellar Space to the Earth, in J. M. Greenberg (ed.), The Chemistry of Life's Origins, Kluwer Academic Publishers, The Netherlands, pp. 195–207.
Griesbeck, A. G. and Meierhenrich, U. J.: 2002, Minireview: Asymmetric Photochemistry and Photochirogenesis, Angew. Chem. Int. Ed. 41, 3147–3154; Kurzaufsatz: Asymmetrische Photochemie und Photochirogenese, Angew. Chem. 114, 3279–3286.
Hazen, R. M., Filley, T. R. and Goodfriend, G. A.: 2001, Selective Adsorption of L-and D-Amino Acids on Calcite: Implications for Biochemical Homochirality, Proc. Nat. Ac. Science 98, 5487–5490.
Jorissen, A. and Cerf, C.: 2002, Asymmetric Photoreactions as the Origin of Biomolecular Homochirality: A Critical Review, Orig. Life Evol. Biosphere 32, 129–142.
Kondepudi, D. K. and Asakura, K.: 2001, Chiral Autocatalysis, Spontaneous Symmetry Breaking, and Stochastic Behaviour, Acc. Chem. Res. 34, 946–954.
Kuhn, W. and Braun, E.: 1929, Photochemische Erzeugung optisch aktiver Stoffe, Die Naturwissenschaften 17, 227–228.
Kuhn, W. and Knopf, E.: 1930, Photochemische Erzeugung optisch aktiver Stoffe, Die Naturwissenschaften 18, 183.
Meierhenrich, U., Thiemann, W. H. P. and Rosenbauer H.: 1999, Molecular Parity Violation via Comets? Chirality 11, 575–582
Meierhenrich, U., Barbier, B., Jacquet, R., Chabin, A., Alcaraz, A., Nahon, L. and Brack, A.: 2001a, Photochemical Origin of Biomolecular Asymmetry, in P. Ehrenfreund, O. Angerer, B. Battrick (eds.), Exo-/Astro-Biology, European Space Agency, ESA SP-496, Noordwijk, The Netherlands, pp. 167–170.
Meierhenrich, U., Thiemann, W. H.-P. and Rosenbauer, H.: 2001b, Pyrolytic Methylation Assisted Enantioseparation of Chiral Hydroxycarboxylic Acids, J. Anal. Appl. Pyrolysis 60, 13–26.
Meierhenrich, U. J., Thiemann, W. H.-P., Goesmann, F., Roll, R. and Rosenbauer, H.: 2001c, Enantiomer Separation of Hydrocarbons in Preparation of Rosetta's ‘Chirality-Experiment,’ Chirality 13, 454–457.
Meierhenrich, U. J., Thiemann, W. H.-P., Muñoz Caro, G. M., Schutte, W. A. and Greenberg, J. M.: 2001d, Simulated Cometary Matter as a Test for Enantiomer Separating Chromatography for Use on Comet 46P/Wirtanen, Adv. Space Res. 27, 329–334.
Meierhenrich, U. J. Thiemann W. H.-P. and Rosenbauer, H.: 2001e, Stereochemical Investigations of Cometary Matter Onboard the ROSETTA Lander, Enantiomer 6, 97–99.
Meierhenrich, U. J., Thiemann, W. H.-P., Goesmann, F., Roll, R. and Rosenbauer, H.: 2003a, Enantioselective Amino Acid Analysis in Cometary Matter Planned for the COSAC Instrument Onboard Rosetta Lander, in H. Sawaya-Lacoste (ed.), Exo-/Astro-Biology, European Space Agency, ESA SP-518, Noordwijk, The Netherlands, pp. 477–478.
Meierhenrich, U. J., Nguyen, M.-J., Barbier, B., Brack, A. and Thiemann, W.H.-P: 2003b, Resolution of Saturated Aliphatic Hydrocarbon Enantiomers on Permethylated β-Cyclodextrin, Chirality, submitted.
Mendoza-Gomez, C. X. and Greenberg, J. M.: 1991, Laboratory Studies of Grain mantles in Interstellar Space, in A. C. Levasseur-Regourd and H. Hasegawa (eds.), Origins and Evolution of Interplanetary Dust, Kluwer, pp. 437–440.
Moradpour, A., Nicoud, J. F., Balavoine, G., Kagan, H. and Tsoucaris, G.: 1971, Photochemistry with Circularly Polarized Light. The Synthesis of Optically Active Hexahelicene, J. Am. Chem. Soc. 93, 2353–2354.
Muñoz Caro, G. M., Meierhenrich, U. J., Schutte, W. A., Barbier, B., Arcones Segovia, A., Rosenbauer, H., Thiemann, W. H.-P., Brack, A. and Greenberg, J. M.: 2002, Amino Acids from Ultraviolet Irradiation of Interstellar Ice Analogues, Nature 416, 403–406.
Muñoz Caro, G. M., Meierhenrich, U. J., Schutte, W. A., Greenberg, J. M. and Thiemann, W.: 2003, UV-Photoprocessing of Interstellar Ice Analogs: Formation of HMT Derivatives, Astron. Astrophys., in print.
Musigmann, M., Busalla, A., Blum, K. and Thompson, D. G.: 1999, Asymmetries in Collisions between Electrons and Oriented Chiral Molecules, J. Phys. B: At.Mol. Opt. Phys. 32, 4117–4128.
Ribó, J. M., Crusats, J., Sagués, F., Claret, J. and Rubires, R.: 2001, Chiral Sign Induction by Vortices during the Formation of Mesophases in Stirred Solutions, Science 292, 2063–2066.
Rosenbauer, H., Goesmann, F., Roll, R., Raulin, F., Szopa, C., Coscia, D., Israel, G., Brun, F., Thiemann, W., Meierhenrich, U. and Wollnik, H.: 2002, The COSAC experiment. European Space Agency, ESA SP-1165, The Netherlands, in print.
Snyder, P. A., Vipond, P. M. and Curtis Johnson, W.: 1973, Circular Dichroism of the Alkyl Amino Acids in the Vacuum Ultraviolet, Biopolymers 12, 975–992.
Soai, K., Osanai, S., Kadowaki, K., Yonekubo, S., Shibata, T. and Sato, I.: 1999, d-and l-Quartz-Promoted Highly Enantioselective Synthesis of a Chiral Organic Compound, J. Am. Chem. Soc. 121, 11235–11236.
Szopa, C. et al.: 2002, Gas Chromatography for in situ Analysis of a Cometary Nucleus IV. Study of Capillary Column Robustness for Space Application, J. Chrom. A 982, 303–312.
Thiemann, W. and Meierhenrich, U.: 2001a, Analysis of Enantioenrichments in Cometary Matter by Rosetta/RoLand, in P. Ehrenfreund, O. Angerer, B. Battrick (eds.), Exo-/Astro-Biology, European Space Agency, ESA SP-496, Noordwijk, The Netherlands, pp. 99–102.
Thiemann, W. H.-P. and Meierhenrich, U.: 2001b, ESA Mission ROSETTA Will Probe for Chirality of Cometary Amino Acids, Orig. Life Evol. Biosphere 31, 199–210.
Thiemann, W. H.-P., Rosenbauer, H. and Meierhenrich, U. J.: 2001c, Conception of the ‘Chirality-Experiment’ on ESA's Mission ROSETTA to Comet 46P/Wirtanen, Adv. Space Res. 27, 323–328.
Yamagata, Y.: 1966, A Hypothesis for the Asymmetric Appearance of Biomolecules on Earth, J. Theoret. Biol. 11, 495–498.
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Meierhenrich, U.J., Thiemann, W.HP. Photochemical Concepts on the Origin of Biomolecular Asymmetry. Orig Life Evol Biosph 34, 111–121 (2004). https://doi.org/10.1023/B:ORIG.0000009832.71546.1d
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DOI: https://doi.org/10.1023/B:ORIG.0000009832.71546.1d