Stability of racemic and chiral steady states in open and closed chemical systems

Ribó, Josep M.; Hochberg, David

doi:10.1016/j.physleta.2008.10.079

Cited by 33 publications

(49 citation statements)

References 40 publications

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“…The influence of the time dependent order parameter ee(t) on the rates of both racemization and deracemization is neglected here for simplicity: the deracemization, for example, is fastest, when (for a given total concentration [Q]), the autocatalyst is enantiopure (ee=100%), because the difference in concentration of the more abundant enantiomer to the less abundant form grows most rapidly then. However, racemization is fastest, too, when the displacement of the reaction mixture from the racemic (kinetic and thermodynamic) equilibrium state (Ribo and Hochberg 2008) is maximal (i.e. again for ee = 100%), because the enantiomerization of the more abundant into the less abundant enantiomer is then not counterbalanced by an enantiomerization in the reverse direction.…”

Section: Non-linear Autocatalytic Reaction Networkmentioning

confidence: 99%

Spontaneous Mirror Symmetry Breaking in the Aldol Reaction and its Potential Relevance in Prebiotic Chemistry

Mauksch

Wei

Freund

et al. 2009

Orig Life Evol Biosph

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The origin of the single chirality of most biomolecules is still a great puzzle. Carbohydrates could form in the formose reaction, which is proposed to be autocatalytic and contains aldol reaction steps. Based on our earlier observation of organoautocatalysis and spontaneous enantioenrichment in absence of deliberate chiral influences in the aldol reaction of acetone and p-nitrobenzaldehyde we suggest that a similar effect might be present also in the aldol reactions involved in gluconeogenesis. Herein we show that reactant precipitation observed in our earlier reported experiments does not affect the asymmetric autocatalysis in the aldol reaction we studied. We explain the phenomenon of spontaneous mirror symmetry breaking in such organocatalytic homogenous systems qualitatively by non-linear reaction network kinetics and classical transition state theory.

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Section: Non-linear Autocatalytic Reaction Networkmentioning

confidence: 99%

Spontaneous Mirror Symmetry Breaking in the Aldol Reaction and its Potential Relevance in Prebiotic Chemistry

Mauksch

Wei

Freund

et al. 2009

Orig Life Evol Biosph

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“…This makes it impossible to determine if different models, which appeal to the same physical phenomena (symmetry-breaking and enantiomeric enrichment, in our case), belong to the same qualitative universality class even though they may differ quantitatively, as is reasonably expected. Some earlier authors have derived dynamical models for enantiomeric enrichment, which are claimed to contain the symmetry-breaking pitchfork bifurcation (e.g., Ribó and Hochberg (2008)). Yet the pitchfork is a degenerate bifurcation, which is non-persistent to perturbation.…”

Section: Modelling the Growth Of Chirality From A Small Enantiomeric mentioning

confidence: 99%

The Life Story of Hydrogen Peroxide III: Chirality and Physical Effects at the Dawn of Life

Ball

Brindley

2015

Orig Life Evol Biosph

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It is a remarkable observed fact that all life on Earth is homochiral, its biology using exclusively the D-enantiomer of ribose, the sugar moiety of the ribonucleic acids, and the L-enantiomers of the chiral amino acids. Motivated by concurrent work that elaborates further the role of hydrogen peroxide in providing an oscillatory drive for the RNA world (Ball & Brindley 2015a, J. R. Soc. Interface 12, 20150366, and Ball & Brindley 2015b, this journal, in press), we reappraise the structure and physical properties of this small molecule within this context. Hydrogen peroxide is the smallest, simplest molecule to exist as a pair of non-superimposable mirror images, or enantiomers, a fact which leads us to develop the hypothesis that its enantiospecific interactions with ribonucleic acids led to enantioselective outcomes. We propose a mechanism by which these chiral interactions may have led to amplification of D-ribonucleic acids and extinction of L-ribonucleic acids.

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“…The LES network cannot lead to absolute asymmetric synthesis, due to the microreversibility principle, when it is composed of the three reactions (I) + (II) + (III rac ) (see ref. [13]). However, it leads to SMSB in a compartmentalized system at different temperatures.…”

Section: à2mentioning

confidence: 99%

“…In fact, it has been shown [13] that LES in a closed system does not lead to SMSB, nor can it lead to a temporary and resistant amplification [14] of the initial ee, such as those that can be obtained in Frank-like networks for relatively high exergonic reactions.…”

Section: Introductionmentioning

confidence: 99%

Spontaneous Emergence of Chirality in the Limited Enantioselectivity Model: Autocatalytic Cycle Driven by an External Reagent

et al. 2013

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The model of limited enantioselectivity (LES) in closed systems, and under experimental conditions able to achieve chemical equilibrium, can give rise to neither spontaneous mirror symmetry breaking (SMSB) nor kinetic chiral amplifications. However, it has been recently shown that it is able to lead to SMSB, as a stationary final state, in thermodynamic scenarios involving nonuniform temperature distributions and for compartmentalized separation between the two autocatalytic reactions. Herein, it is demonstrated how SMSB may occur in LES in a cyclic network with uniform temperature distribution if the reverse reaction of the nonenantioselective autocatalysis, which gives limited inhibition on the racemic mixture, is driven by an external reagent, that is, in conditions that keep the system out of chemical equilibrium. The exact stability analysis of the racemic and chiral final outcomes and the study of the reaction parameters leading to SMSB are resolved analytically. Numerical simulations, using chemical kinetics equations, show that SMSB may occur for chemically reasonable parameters. Numerical simulations on SMSB are also presented for speculative, but reasonable, scenarios implying reactions common in amino acid chemistry.

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Stability of racemic and chiral steady states in open and closed chemical systems

Cited by 33 publications

References 40 publications

Spontaneous Mirror Symmetry Breaking in the Aldol Reaction and its Potential Relevance in Prebiotic Chemistry

Spontaneous Mirror Symmetry Breaking in the Aldol Reaction and its Potential Relevance in Prebiotic Chemistry

The Life Story of Hydrogen Peroxide III: Chirality and Physical Effects at the Dawn of Life

Spontaneous Emergence of Chirality in the Limited Enantioselectivity Model: Autocatalytic Cycle Driven by an External Reagent

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