Modeling spontaneous chiral symmetry breaking and deracemization phenomena: Discrete versus continuum approaches

Blanco, Celia; Ribó, Josep M.; Hochberg, David

doi:10.1103/physreve.91.022801

Cited by 21 publications

(31 citation statements)

References 75 publications

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“…Dissociation into monomers and nonlinear effect due to the cluster incorporation to crystals correspond to Saito and Hyuga's general conditions for realizing homochirality [19]. The time-evolution of cluster size distribution was studied from different view points [20][21][22][23][24] and all proved the role of chiral clusters to provide the exponential amplification of CEE.…”

Section: Introductionmentioning

confidence: 78%

Mechanism of chirality conversion by periodic change of temperature: Role of chiral clusters

Katsuno

Uwaha

2016

Phys. Rev. E

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By grinding crystals in a solution, the chirality of crystal structure (and the molecular chirality for the case of chiral molecules as well) can be converted, and the cause of the phenomenon is attributed to crystal growth with chiral clusters. We show that the recently found chirality conversion with a periodic change of temperature can also be explained by crystal growth with chiral clusters. With the use of a generalized Becker-Döring model, which includes enantio-selective incorporation of small chiral clusters to large solid clusters, the change of cluster distribution and the mass flow between clusters are studied. The chiral clusters act as a reservoir to pump out the minority species to the majority, and the exponential amplification of the enantiomeric excess found in the experiment is reproduced in the numerical calculation.

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Section: Introductionmentioning

confidence: 78%

Mechanism of chirality conversion by periodic change of temperature: Role of chiral clusters

Katsuno

Uwaha

2016

Phys. Rev. E

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“…A principle case in point is when the methodologies used from systems biology, where irreversible transformations of complex species occur, are translated to chemical reactions [62]. We may say that living species are born and die, but chemical compounds in a reaction network are born, can die and can also be 'resurrected' thanks to inverse reaction pathways.…”

Section: Abiotic Track Towards Biological Homochiralitymentioning

confidence: 99%

Spontaneous mirror symmetry breaking and origin of biological homochirality

Ribó

Hochberg

Crusats

et al. 2017

J. R. Soc. Interface.

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Recent reports on both theoretical simulations and on the physical chemistry basis of spontaneous mirror symmetry breaking (SMSB), that is, asymmetric synthesis in the absence of any chiral polarizations other than those arising from the chiral recognition between enantiomers, strongly suggest that the same nonlinear dynamics acting during the crucial stages of abiotic chemical evolution leading to the formation and selection of instructed polymers and replicators, would have led to the homochirality of instructed polymers. We review, in the first instance, which reaction networks lead to the nonlinear kinetics necessary for SMSB, and the thermodynamic features of the systems where this potentiality may be realized. This could aid not only in the understanding of SMSB, but also the design of reliable scenarios in abiotic evolution where biological homochirality could have taken place. Furthermore, when the emergence of biological chirality is assumed to occur during the stages of chemical evolution leading to the selection of polymeric species, one may hypothesize on a tandem track of the decrease of symmetry order towards biological homochirality, and the transition from the simple chemistry of astrophysical scenarios to the complexity of systems chemistry yielding Darwinian evolution.

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“…Monte Carlo simulations 35,[42][43][44] , dispersive kinetic models 45 and population balance models [46][47][48][49] .…”

Section: Introductionmentioning

confidence: 99%

Coupling Viedma Ripening with Racemic Crystal Transformations: Mechanism of Deracemization

Xiouras

Horst

Gerven

et al. 2017

Crystal Growth & Design

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It has been recently observed that coupling Viedma ripening with a seeded in-situ metastable racemic crystal to conglomerate transformation leads to accelerated and complete deracemization: crystal transformation-enhanced deracemization. By means of a simple kinetic model, we show that the mechanistic pathway of this new process depends profoundly on the interplay between the crystal transformation and racemization processes, which in turn influence the nucleation process of the counter enantiomer. If the nucleation of the counter enantiomer is suppressed (e.g. by sufficiently fast racemization, low amount of racemic compound or gradual feed, low relative solubility between racemic compound and conglomerate), deracemization proceeds via a second order asymmetric transformation (SOAT) and is limited primarily by the dissolution rate of the racemic crystals and the growth rate of the preferred enantiomer crystals. Breakage and agglomeration accelerate the process, but contrary to conventional Viedma ripening, they are not essential ingredients to explain the observed enantiomeric enrichment. If the nucleation process of the counter enantiomer is not sufficiently suppressed, deracemization is initially controlled by the dissolution rate of the racemic crystals, but Viedma ripening is subsequently required to convert the conglomerate crystals of the counter enantiomer formed by nucleation, resulting in slower deracemization kinetics. In both cases, the combined process leads to faster deracemization kinetics compared to conventional Viedma ripening, while it autocorrects for the main disadvantage of SOAT, i.e. the accidental nucleation of the counter enantiomer. In addition, crystal transformation-enhanced deracemization extends the range of applicability of solid-state deracemization processes to compounds that form metastable racemic crystals. interplay between the crystal transformation and racemization processes, which in turn influence the nucleation process of the counter enantiomer. If the nucleation of the counter enantiomer is 3 suppressed (e.g. by sufficiently fast racemization, low amount of racemic compound or gradual feed, low relative solubility between racemic compound and conglomerate), deracemization proceeds via a second order asymmetric transformation (SOAT) and is limited primarily by the dissolution rate of the racemic crystals and the growth rate of the preferred enantiomer crystals.Breakage and agglomeration accelerate the process, but contrary to conventional Viedma ripening, they are not essential ingredients to explain the observed enantiomeric enrichment. If the nucleation process of the counter enantiomer is not sufficiently suppressed, deracemization is initially controlled by the dissolution rate of the racemic crystals, but Viedma ripening is subsequently required to convert the conglomerate crystals of the counter enantiomer formed by nucleation, resulting in slower deracemization kinetics. In both cases, the combined process leads to faster deracemization kinetics compared ...

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Modeling spontaneous chiral symmetry breaking and deracemization phenomena: Discrete versus continuum approaches

Cited by 21 publications

References 75 publications

Mechanism of chirality conversion by periodic change of temperature: Role of chiral clusters

Mechanism of chirality conversion by periodic change of temperature: Role of chiral clusters

Spontaneous mirror symmetry breaking and origin of biological homochirality

Coupling Viedma Ripening with Racemic Crystal Transformations: Mechanism of Deracemization

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