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Spontaneous Emergence of Chirality in the Limited Enantioselectivity Model: Autocatalytic Cycle Driven by an External Reagent
Author(s) -
Blanco Celia,
Crusats Joaquim,
ElHachemi Zoubir,
Moyano Albert,
Hochberg David,
Ribó Josep M.
Publication year - 2013
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201300350
Subject(s) - autocatalysis , reagent , chemistry , chirality (physics) , chemical reaction , chemical equilibrium , autocatalytic reaction , chemical stability , kinetics , chemical kinetics , thermodynamics , thermodynamic equilibrium , steady state (chemistry) , chemical physics , computational chemistry , symmetry breaking , statistical physics , catalysis , physics , chiral symmetry breaking , organic chemistry , classical mechanics , quantum mechanics , nambu–jona lasinio model
Abstract The model of limited enantioselectivity (LES) in closed systems, and under experimental conditions able to achieve chemical equilibrium, can give rise to neither spontaneous mirror symmetry breaking (SMSB) nor kinetic chiral amplifications. However, it has been recently shown that it is able to lead to SMSB, as a stationary final state, in thermodynamic scenarios involving nonuniform temperature distributions and for compartmentalized separation between the two autocatalytic reactions. Herein, it is demonstrated how SMSB may occur in LES in a cyclic network with uniform temperature distribution if the reverse reaction of the nonenantioselective autocatalysis, which gives limited inhibition on the racemic mixture, is driven by an external reagent, that is, in conditions that keep the system out of chemical equilibrium. The exact stability analysis of the racemic and chiral final outcomes and the study of the reaction parameters leading to SMSB are resolved analytically. Numerical simulations, using chemical kinetics equations, show that SMSB may occur for chemically reasonable parameters. Numerical simulations on SMSB are also presented for speculative, but reasonable, scenarios implying reactions common in amino acid chemistry.