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Cited by 6Origins and Evolution of LifeAnalytical Chemistry and ChromatographyCalcium Carbonate Crystallization and Inhibition

Racemate Resolution of Alanine and Leucine on Homochiral Quartz, and Its Alteration by Strong Radiation Damage

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Garcia, Adrien D., Meinert, Cornelia, Finger, Friedrich, Meierhenrich, Uwe J., Hejl, Ewald·2021·Life
DOI 10.3390/life11111222PMC PMC8622614
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Abstract

Homochiral proteins orchestrate biological functions throughout all domains of life, but the origin of the uniform l-stereochemistry of amino acids remains unknown. Here, we describe enantioselective adsorption experiments of racemic alanine and leucine onto homochiral d- and l-quartz as a possible mechanism for the abiotic emergence of biological homochirality. Substantial racemate resolution with enantiomeric excesses of up to 55% are demonstrated to potentially occur in interstitial pores, along grain boundaries or small fractures in local quartz-bearing environments. Our previous hypothesis on the enhanced enantioselectivity due to uranium-induced fission tracks could not be validated. Such capillary tubes in the near-surface structure of quartz have been proposed to increase the overall chromatographic separation of enantiomers, but no systematic positive correlation of accumulated radiation damage and enantioselective adsorption was observed in this study. In general, the natural l-quartz showed stronger enantioselective adsorption affinities than synthetic d-quartz without any significant trend in amino acid selectivity. Moreover, the l-enantiomer of both investigated amino acids alanine and leucine was preferably adsorbed regardless of the handedness of the enantiomorphic quartz sand. This lack of mirror symmetry breaking is probably due to the different crystal habitus of the synthetic z-bar of d-quartz and the natural mountain crystals of l-quartz used in our experiments.

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  • Garcia et al. demonstrated an experimentally significant deracemization (1-55%) of racemic alanine and leucine solutions on homochiral quartz sand.

    “In a 2021 paper, Garcia et al. demonstrated an experimentally significant deracemization (1-55%) of racemic alanine and leucine solutions on homochiral quartz sand. (Garcia et al., 2021)”

    From The Origin and Early Evolution of Life: Homochirality Emergence in Prebiotic Environments (2023) · cites this paper as Garcia et al., 2021

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References 44 · Cited by 6

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  1. [1]Wächtershäuser G. Biomolecules: The origin of their optical activity Med. Hypotheses 1991 36 307 311 10.1016/0306-9877(91)90001-F 1809848 · DOI
  2. [2]Klabunovskii E.I. Can Enantiomorphic Crystals Like Quartz Play a Role in the Origin of Homochirality on Earth? Astrobiology 2001 1 127 131 10.1089/153110701753198891 12467116 · DOI · Paper page
  3. [3]Meierhenrich U.J. Amino Acids and the Asymmetry of Life Advances in Astrobiology and Biogeophysics Springer Berlin/Heidelberg, Germany 2008 978-3-540-76886-9
  4. [4]Idelson M. Blout E.R. Polypeptides. XVIII.1 A Kinetic Study of the Polymerization of Amino Acid N-Carboxyanhydrides Initiated by Strong Bases J. Am. Chem. Soc. 1958 80 2387 2393 10.1021/ja01543a012 · DOI
  5. [6]Joyce G.F. Schwartz A.W. Miller S.L. Orgel L.E. The case for an ancestral genetic system involving simple analogues of the nucleotides Proc. Natl. Acad. Sci. USA 1987 84 4398 4402 10.1073/pnas.84.13.4398 2440020 PMC305096 · DOI · Paper page
  6. [7]Eschenmoser A. The search for the chemistry of life’s origin Tetrahedron 2007 63 12821 12844 10.1016/j.tet.2007.10.012 · DOI · Paper page
  7. [8]Krishnamurthy R. Hud N.V. Introduction: Chemical Evolution and the Origins of Life Chem. Rev. 2020 120 4613 4615 10.1021/acs.chemrev.0c00409 32517476 · DOI
  8. [9]Kondepudi D.K. Kaufman R.J. Singh N. Chiral Symmetry Breaking in Sodium Chlorate Crystallization Science 1990 250 975 976 10.1126/science.250.4983.975 17746924 · DOI · Paper page
  9. [10]Karagunis G. Coumoulos G. A New Method of Resolving a Racemic Compound Nat. Cell Biol. 1938 142 162 163 10.1038/142162a0 · DOI
  10. [11]Bonner W.A. Kavasmaneck P.R. Martin F.S. Flores J.J. Asymmetric Adsorption of Alanine by Quartz Science 1974 186 143 144 10.1126/science.186.4159.143 17744221 · DOI · Paper page
  11. [12]Hazen R.M. Filley T.R. Goodfriend G.A. Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality Proc. Natl. Acad. Sci. USA 2001 98 5487 5490 10.1073/pnas.101085998 11331767 PMC33239 · DOI · Paper page
  12. [13]Quack M. How Important is Parity Violation for Molecular and Biomolecular Chirality? Angew. Chem. Int. Ed. 2002 41 4618 4630 10.1002/anie.200290005 12481315 · DOI · Paper page
  13. [14]Balavoine G. Moradpour A. Kagan H.B. 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. 1974 96 5152 5158 10.1021/ja00823a023 · DOI
  14. [15]Meierhenrich U.J. Filippi J.-J. Meinert C. Hoffmann S.V. Bredehöft J.H. Nahon L. Photolysis of rac-Leucine with Circularly Polarized Synchrotron Radiation Chem. Biodivers. 2010 7 1651 1659 10.1002/cbdv.200900311 20564679 · DOI · Paper page
  15. [16]Meinert C. Hoffmann S.V. Cassam-Chenaï P. Evans A.C. Giri C. Nahon L. Meierhenrich U.J. Photonenergy-Controlled Symmetry Breaking with Circularly Polarized Light Angew. Chem. Int. Ed. 2014 53 210 214 10.1002/anie.201307855 24227543 · DOI · Paper page
  16. [17]Meinert C. Cassam-Chenaï P. Jones N.C. Nahon L. Hoffmann S.V. Meierhenrich U.J. Anisotropy-Guided Enantiomeric Enhancement in AlanineUsing Far-UV Circularly Polarized Light Orig. Life Evol. Biosph. 2015 45 149 161 10.1007/s11084-015-9413-x 25773582 · DOI · Paper page
  17. [19]Rosenberg R.A. Abu Haija M. Ryan P.J. Chiral-Selective Chemistry Induced by Spin-Polarized Secondary Electrons from a Magnetic Substrate Phys. Rev. Lett. 2008 101 178301 10.1103/PhysRevLett.101.178301 18999792 · DOI · Paper page
  18. [20]Hejl E. Are fission tracks in enantiomorphic minerals a key to the emergence of homochirality? Neues Jahrb. Für Mineral. Abh. 2017 194 97 106 10.1127/njma/2017/0049 · DOI
  19. [21]Weiland E.F. Ludwig K.R. Naeser C.W. Simmons E.C. Fission-Track Dating Applied to Uranium Mineralization Master’s Thesis Colorado School of Mines Golden, CO, USA 1979
  20. [22]Cunningham C.G. Ludwig K.R. Naeser C.W. Weiland E.K. Mehnert H.H. Steven T.A. Rasmussen J.D. Geochronology of hydrothermal uranium deposits and associated igneous rocks in the eastern source area of the Mount Belknap Volcanics, Marysvale, Utah Econ. Geol. 1982 77 453 463 10.2113/gsecongeo.77.2.453 · DOI
  21. [23]Vincent D. Clocchiatti R. Langevin Y. Fission-track dating of glass inclusions in volcanic quartz Earth Planet. Sci. Lett. 1984 71 340 348 10.1016/0012-821X(84)90098-0 · DOI
  22. [24]Fleischer R. Price P. Techniques for geological dating of minerals by chemical etching of fission fragment tracks Geochim. Cosmochim. Acta 1964 28 1705 1714 10.1016/0016-7037(64)90017-1 · DOI
  23. [25]Hejl E. Finger F. Chiral Proportions of Nepheline Originating from Low-Viscosity Alkaline Melts. A Pilot Study Symmetry 2018 10 410 10.3390/sym10090410 · DOI
  24. [26]Blichert-Toft J. Arndt N. Ludden J. Precambrian alkaline magmatism Lithos 1996 37 97 111 10.1016/0024-4937(95)00031-3 · DOI
  25. [27]Dryzun C. Mastai Y. Shvalb A. Avnir D. Chiral silicate zeolites J. Mater. Chem. 2009 19 2062 2069 10.1039/b817497k · DOI
  26. [28]Wilde S.A. Valley J. Peck W. Graham C.M. Evidence from detrital zircons for the existence of continental crust and oceans on the Earth 4.4 Gyr ago Nat. Cell Biol. 2001 409 175 178 10.1038/35051550 11196637 · DOI · Paper page
  27. [29]Palache C. Berman G.B. Frondel C. Relative frequencies of Left and Right Quartz The System of Mineralogy J. Wiley New-York New York, NY, USA 1962 Volume 17
  28. [30]Evgenii K. Wolfram T. The role of quartz in the origin of optical activity on earth Orig. Life Evol. Biosph. 2000 30 431 434 10.1023/A:1006766311211 11002889 · DOI · Paper page
  29. [31]Pavlov V.A. Shushenachev Y.V. Zlotin S.G. Chiral and Racemic Fields Concept for Understanding of the Homochirality Origin, Asymmetric Catalysis, Chiral Superstructure Formation from Achiral Molecules, and B-Z DNA Conformational Transition Symmetry 2019 11 649 10.3390/sym11050649 · DOI
  30. [33]Heritsch H. Die Verteilung von Rechts- und Linksquarzen in Schriftgraniten Miner. Pet. 1953 3 115 125 10.1007/BF01120706 · DOI
  31. [34]Hazen R.M. Chapter 11—Chiral Crystal Faces of Common Rock-Forming Minerals Progress in Biological Chirality Pályi G. Zucchi C. Caglioti L. Elsevier Science Ltd. Oxford, UK 2004 137 151 978-0-08-044396-6
  32. [35]Churchill H. Teng H. Hazen R.M. Correlation of pH-dependent surface interaction forces to amino acid adsorption: Implications for the origin of life Am. Miner. 2004 89 1048 1055 10.2138/am-2004-0716 · DOI
  33. [36]Hazen R.M. Presidential Address to the Mineralogical Society of America, Salt Lake City, October 18, 2005: Mineral surfaces and the prebiotic selection and organization of biomolecules Am. Miner. 2006 91 1715 1729 10.2138/am.2006.2289 · DOI
  34. [38]Yogev-Einot D. Avnir D. The temperature-dependent optical activity of quartz: From Le Châtelier to chirality measures Tetrahedron Asymmetry 2006 17 2723 2725 10.1016/j.tetasy.2006.10.004 · DOI
  35. [39]Ersahin S. Gunal H. Kutlu T. Yetgin B. Coban S. Estimating specific surface area and cation exchange capacity in soils using fractal dimension of particle-size distribution Geoderma 2006 136 588 597 10.1016/j.geoderma.2006.04.014 · DOI
  36. [40]Wagner G. Van Den Haute P. Fission-Track Dating Solid Earth Sciences Library Springer Berlin/Heidelberg, Germany 1992 978-94-010-5093-7
  37. [41]Meinert C. Meierhenrich U.J. A New Dimension in Separation Science: Comprehensive Two-Dimensional Gas Chromatography Angew. Chem. Int. Ed. 2012 51 10460 10470 10.1002/anie.201200842 22965886 · DOI · Paper page
  38. [42]Myrgorodska I. Meinert C. Martins Z. D’Hendecourt L.L.S. Meierhenrich U.J. Quantitative enantioseparation of amino acids by comprehensive two-dimensional gas chromatography applied to non-terrestrial samples J. Chromatogr. A 2016 1433 131 136 10.1016/j.chroma.2016.01.014 26803906 · DOI · Paper page
  39. [44]Li W. Wang L. Lang M. Trautmann C. Ewing R.C. Thermal annealing mechanisms of latent fission tracks: Apatite vs. zircon Earth Planet. Sci. Lett. 2011 302 227 235 10.1016/j.epsl.2010.12.016 · DOI
  40. [45]Reineck H.-E. Singh I.B. Depositional Sedimentary Environments: With Reference to Terrigenous Clastics Springer Study Edition 2nd ed. Springer Berlin/Heidelberg, Germany 1980 978-3-540-10189-5

Authors
Garcia, A. D., Meinert, C., Finger, F., Meierhenrich, U. J., & Hejl, E.
Affiliations
  • Centre National de la Recherche Scientifique (FR)
  • University of Salzburg (AT)
Corresponding author
  • Meinert, Cornelia
  • Hejl, Ewald
ORCID
Venue
Life
Publisher
MDPI AG
Published
2021-11-11
Volume
11
Issue
11
Pages
1222
ISSN
2075-1729 (ISSN-L)
DOI
10.3390/life11111222
PMC
PMC8622614
OpenAlex
W3211418069
Cited by
6
References
44
Citations by year
2026: 1 · 2025: 1 · 2024: 1 · 2023: 1 · 2022: 2
FWCI
0.54
Type
journal article
Language
en
Open access
Licence
Locations
  • Life (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • HAL (submittedVersion, other-oa)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
Funders
  • European Research Council (804144)
  • FWF Austrian Science Fund (P 30444-N28)
Topics
  • Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
  • Physical Sciences › Chemistry › Spectroscopy › Analytical Chemistry and Chromatography
  • Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
Keywords
origin of homochirality, enantioselective adsorption, racemic resolution, alanine, leucine, quartz, radiation damage, amino acid chirality, enantiomeric excess, crystal morphology

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