Mechanically induced homochirality in nucleated enantioselective polymerization


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.

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Divisions: College of Engineering & Physical 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
Publication ISSN: 1520-5207
Last Modified: 06 May 2024 07:18
Date Deposited: 24 Jan 2017 08:14
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Related URLs: http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2017-02-09
Published Online Date: 2017-01-10
Accepted Date: 2017-01-10
Submitted Date: 2016-10-24
Authors: Blanco, Celia
Stich, Michael (ORCID Profile 0000-0001-8862-1044)
Hochberg, David



Version: Accepted Version

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