Spontaneous Emergence of Homochirality via Coherently Coupled Antagonistic and Reversible Reaction Cycles
Abstract
Asymmetric synthesis aims at obtaining enantio‐enriched products in stereoselective reactions under a chiral influence. We demonstrate both mathematically and numerically that, even under nominally achiral conditions, fully homochiral steady states can be obtained in open reactive systems by spontaneous mirror‐symmetry breaking in the homogenous solution phase when the autocatalytic reaction network is closed in the form of coherently coupled antagonistic reversible reaction cycles which, paradoxically, allow for complete recycling of the reactant. We show that the fully reversible Frank mechanism for spontaneous mirror‐symmetry breaking is closely related to the Lotka–Volterra system, which models predator–prey relations in ecosystems. Amplification of total enantiomeric excess and the principle of microscopic reversibility are not in conflict for all conceivable reactions. A viable and widely applicable reaction protocol is introduced and discussed, and it permits the theoretical implications to be applied to practical laboratory examples. Implications for the possible origin of biological homochirality on early earth are discussed.
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The key to overcoming the elusive search for prebiotic reactions with autocatalysis/replication and chiral amplification may lie in the establishment of self-organized connected catalytic cycles, i.e., protometabolic networks.
“In order to overcome this elusive search for prebiotic reactions that present autocatalysis/replication with chiral amplification, as suggested by Blackmond,60 the key may lie in the establishment of self-organized connected catalytic cycles,207i.e., in the type of protometabolic networks reviewed above.”
From The protometabolic nature of prebiotic chemistry (2023) · cites this paper as [207]
Cites
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Frank Model and Spontaneous Emergence of Chirality in Closed Systems
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Spontaneous mirror symmetry breaking and origin of biological homochirality
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The protometabolic nature of prebiotic chemistry
Nogal, N., Sanz-Sánchez, M., Vela-Gallego, S., Ruiz-Mirazo, K., & de la Escosura, A. (2023) · Chemical Society Reviews · doi:10.1039/d3cs00594a · Cited by 61 · see citing works
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- Authors
- Mauksch, M., & Tsogoeva, S. B.
- Affiliations
- Friedrich-Alexander-Universität Erlangen-Nürnberg (DE)
- Venue
- ChemPhysChem
- Publisher
- Wiley
- Published
- 2008-10-31
- Volume
- 9
- Issue
- 16
- Pages
- 2359-2371
- ISSN
- 1439-4235 (ISSN-L)
- 1439-7641
- OpenAlex
- W2099542709
- Cited by
- 46
- References
- 10
- Citations by year
- 2023: 1 · 2022: 1 · 2020: 3 · 2019: 4 · 2018: 2 · 2017: 2 · 2016: 3 · 2015: 3 · 2014: 2 · 2013: 4 · 2012: 3
- FWCI
- 3.50
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- ChemPhysChem (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
- Physical Sciences › Chemistry › Organic Chemistry › Asymmetric Synthesis and Catalysis
- Physical Sciences › Computer Science › Computer Networks and Communications › Nonlinear Dynamics and Pattern Formation
- Keywords
- homochirality, spontaneous symmetry breaking, mirror symmetry breaking, autocatalytic reaction networks, enantiomeric excess, Lotka-Volterra model, origin of homochirality, early Earth, asymmetric synthesis, microscopic reversibility
- MeSH terms
- Algorithms, Catalysis, Kinetics, Models, Chemical, Stereoisomerism, Thermodynamics, Molecular Structure
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