Selective adsorption of l- and d-amino acids on calcite: Implications for biochemical homochirality

The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO3), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

[1]  K. Soai,et al.  d- and l-Quartz-Promoted Highly Enantioselective Synthesis of a Chiral Organic Compound , 1999 .

[2]  C. Klein.  The geology of North America—An overview , 1992 .

[3]  R. D. Cody,et al.  Chiral habit modifications of gypsum from epitaxial-like adsorption of stereospecific growth inhibitors , 1991 .

[4]  D. Bish,et al.  Crystal structures and cation sites of the rock-forming minerals , 1988 .

[5]  S. Pizzarello,et al.  Non-racemic amino acids in the Murray and Murchison meteorites. , 2000, Geochimica et cosmochimica acta.

[6]  Carl Sagan,et al.  Endogenous production, exogenous delivery and impact-shock synthesis of organic molecules: an inventory for the origins of life , 1992, Nature.

[7]  D. Sholl.  Adsorption of Chiral Hydrocarbons on Chiral Platinum Surfaces , 1998 .

[8]  A. Bally,et al.  The Geology of North America: An Overview , 1989 .

[9]  S. Weiner,et al.  Design strategies in mineralized biological materials , 1997 .

[10]  J. Hough,et al.  Circular polarization in star-formation regions: implications for biomolecular homochirality. , 1998, Science.

[11]  V. V. Kuz'min,et al.  Handedness, origin of life and evolution. , 1991, Physics today.

[12]  D P Glavin,et al.  Amino acids in the Martian meteorite Nakhla. , 1999, Proceedings of the National Academy of Sciences of the United States of America.

[13]  Edward Salisbury Dana,et al.  A Textbook of Mineralogy , 1991 .

[14]  S. Miller.  A production of amino acids under possible primitive earth conditions. , 1953, Science.

[15]  P. Dove,et al.  Thermodynamics of calcite growth: baseline for understanding biomineral formation , 1998, Science.

[16]  Hans-Peter Schertl,et al.  Geochim. cosmochim. acta , 1989 .

[17]  Indraneel Ghosh,et al.  Selective amplification by auto- and cross-catalysis in a replicating peptide system , 1998, Nature.

[18]  S. Pizzarello,et al.  Enantiomeric Excesses in Meteoritic Amino Acids , 1997, Science.

[19]  D. Sumner.  Carbonate precipitation and oxygen stratification in late Archean seawater as deduced from facies and stratigraphy of the Gamohaan and Frisco formations, Transvaal Supergroup, South Africa , 1997 .

[20]  G. Goodfriend.  Patterns of racemization and epimerization of amino acids in land snail shells over the course of the Holocene , 1991 .

[21]  Yohei Yokobayashi,et al.  Emergence of symbiosis in peptide self-replication through a hypercyclic network , 1997, Nature.

[22]  Richard I. Hartley,et al.  Chirality , 2004, International Journal of Computer Vision.

[23]  W. L. Marshall,et al.  Hydrothermal synthesis of amino acids , 1994 .

[24]  N. Lahav,et al.  Biogenesis: Theories of Life's Origin , 1999 .

[25]  V. Davankov.  The nature of chiral recognition: Is it a three‐point interaction? , 1997 .

[26]  J. Ferris,et al.  Template-directed synthesis using the heterogeneous templates produced by montmorillonite catalysis. A possible bridge between the prebiotic and RNA worlds. , 1997, Journal of the American Chemical Society.

[27]  C. Mcfadden,et al.  Adsorption of Chiral Alcohols on “Chiral” Metal Surfaces , 1996 .