Mechanically induced homochirality in nucleated enantioselective polymerization

Blanco, Celia, Stich, Michael and Hochberg, David (2017). Mechanically induced homochirality in nucleated enantioselective polymerization. Journal of Physical Chemistry: Part B, 121 (5), 942–955.


Understanding how biological homochirality may have emerged during chemical evolution remains a challenge for origin of life research. In keeping with this goal, we introduce and solve numerically a kinetic rate equation model of nucleated cooperative enantioselective polymerization in closed systems. The microreversible scheme includes (i) solution phase racemization of the monomers, (ii) linear chain growth by stepwise monomer attachment, in both the nucleation and elongation phases, and (iii) annealing or fusion of homochiral chains. Mechanically induced breakage of the longest chains maintains the system out of equilibrium and drives a breakage-fusion recycling mechanism. Spontaneous mirror symmetry breaking (SMSB) can be achieved starting from small initial enantiomeric excesses due to the intrinsic statistical fluctuations about the idealized racemic composition. The subsequent chiral amplification confirms the model’s capacity for absolute asymmetric synthesis, and without chiral cross-inhibition and without explicit autocatalysis.

Publication DOI:
Divisions: Engineering & Applied Sciences > Mathematics
Engineering & Applied Sciences > Systems analytics research institute (SARI)
Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry B, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see DOI 10.1021/acs.jpcb.6b10705.
Uncontrolled Keywords: Surfaces, Coatings and Films,Physical and Theoretical Chemistry,Materials Chemistry
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Related URLs: http://www.scop ... tnerID=8YFLogxK (Scopus URL)
Published Date: 2017-02-09
Authors: Blanco, Celia
Stich, Michael ( 0000-0001-8862-1044)
Hochberg, David



Version: Accepted Version

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