Chiral polymerization: symmetry breaking and entropy production in closed systems

Literature Information

Publication Date 2010-11-08
DOI 10.1039/C0CP00992J
Impact Factor 3.676
Authors

Celia Blanco, David Hochberg


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Abstract

We solve numerically a kinetic model of chiral polymerization in systems closed to matter and energy flow, paying special attention to its ability to amplify the small initial enantiomeric excesses due to the internal and unavoidable statistical fluctuations. The reaction steps are assumed to be reversible, implying a thermodynamic constraint among some of the rate constants. Absolute asymmetric synthesis is achieved in this scheme. The system can persist for long times in quasi-stationary chiral asymmetric states before racemizing. Strong inhibition leads to long-period chiral oscillations in the enantiomeric excesses of the longest homopolymer chains. We also calculate the entropy production σ per unit volume and show that σ increases to a peak value either before or in the vicinity of the chiral symmetry breaking transition.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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