Mechanically induced homochirality in nucleated enantioselective polymerization

Celia Blanco, Michael Stich, David Hochberg*

*Corresponding author for this work

Research output: Contribution to journalArticle

Abstract

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.
Original languageEnglish
Pages (from-to)942–955
Number of pages14
JournalJournal of Physical Chemistry: Part B
Volume121
Issue number5
Early online date10 Jan 2017
DOIs
Publication statusPublished - 9 Feb 2017

Fingerprint

Fusion reactions
polymerization
Monomers
Polymerization
monomers
fusion
autocatalysis
Amplification
Recycling
Elongation
Mirrors
Nucleation
Annealing
recycling
elongation
Kinetics
attachment
broken symmetry
Chemical analysis
nucleation

Bibliographical note

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.

Cite this

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abstract = "Understanding how biological homochirality may have emerged during chemicalevolution 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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Mechanically induced homochirality in nucleated enantioselective polymerization. / Blanco, Celia; Stich, Michael; Hochberg, David.

In: Journal of Physical Chemistry: Part B, Vol. 121, No. 5, 09.02.2017, p. 942–955.

Research output: Contribution to journalArticle

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