Chiral symmetry breaking and complete chiral purity by thermodynamic-kinetic feedback near equilibrium: implications for the origin of biochirality.
Chiral symmetry breaking occurs when a physical or chemical process spontaneously generates a large excess of one of the two enantiomers--left-handed (L) or right-handed (D)--with no preference as to which of the two enantiomers is produced. From the viewpoint of energy, these two enantiomers can exist with an equal probability, and inorganic processes that involve chiral products commonly yield a racemic mixture of both. The fact that biologically relevant molecules exist only as one of the two enantiomers is a fascinating example of complete symmetry breaking in chirality and has long intrigued the science community. The origin of this selective chirality has remained a fundamental enigma with regard to the origin of life since the time of Pasteur, some 140 years ago. Here, it is shown that two populations of chiral crystals of left and right hand cannot coexist in solution: one of the chiral populations disappears in an irreversible autocatalytic process that nurtures the other one. Final and complete chiral purity seems to be an inexorable fate in the course of the common process of growth-dissolution. This unexpected chiral symmetry breaking can be explained by the feedback between the thermodynamic control of dissolution and the kinetics of the growth process near equilibrium. This "thermodynamic-kinetic feedback near equilibrium" is established as a mechanism to achieve complete chiral purity in solid state from a previously solid racemic medium. The way in which this mechanism could operate in solutions of chiral biomolecules is described. Finally, based on this mechanism, experiments designed to search for chiral purity in a new way are proposed: chiral purity of amino acids or biopolymers is predicted in solid phase from a previously solid racemic medium. This process may have played a key role in the origin of biochirality.
Viedma
Cristobal
C
Departamento de Cristalografia y Mineralogía, Facultad de Geología, Universidad Complutense, Ciudad Universitaria, Madrid, Spain. viedma@geo.ucm.es
D001959:Bromates / Q000737:chemistry*; D003460:Crystallization; D005246:Feedback / Q000502:physiology; D007700:Kinetics; D017670:Sodium Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D013816:Thermodynamics
D001959:Bromates; D017670:Sodium Compounds; C060553:sodium bromate