Energy threshold for chiral symmetry breaking in molecular self-replication

Hawbaker, Neil; Blackmond, Donna G.

doi:10.1038/s41557-019-0321-y

“…[13] In addition, recently the Soai autocatalytic reaction system was tested to detect the energy imbalance that gives rise to directed symmetry breaking. [14] We have recently reported on the combination of autocatalysis with remote amplification of chirality. [15] Notably, we introduced pyridinyl alkanols 4 as a new autocatalytic family and their amplification in parallel with pyrimidinyl alkanol 2.…”

mentioning

confidence: 99%

Absolute Autocatalytic Amplification under Heterogenous Phase Conditions Involving Subsequent Hydride Transfer and a Hemiacetal Intermediate

Rotunno

¹

,

Petersen

²

,

Amedjkouh

³

2020

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In contrast to the homogenous phase, absolute asymmetric amplification of pyridine alkanol is observed under heterogenous conditions. The reaction of iPr2Zn vapor on a solid powder of pyridine carbaldehyde induced autocatalytic amplification of chirality providing the alkanol product with an enantiopurity up to 90 % ee. In this study, side products were identified and their formation is traced back to redox pathways involving hydride transfer, namely a chiral ester resulting most probably from a disproportionation of the starting aldehyde into a hemiacetal and subsequent hydride loss following a Claisen‐Tishchenko mechanism. These observations provide new perspectives in the elucidation of the mechanism of amplification of chirality in the Soai reaction.

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“…Enantiopure additives have been shown to direct the symmetry breaking in the Soai reaction to the same absolute configuration. [3,4,5] However, the mechanism of the Soai reaction is unique and its principles cannot be extended to prebiotic systems.…”

Section: Chiralsymmetrybreakingispartandparcelofdiscussionofmentioning

confidence: 99%

Enantiospecific Solid Solution Formation Triggers the Propagation of Homochirality

Baglai

¹

,

Leeman

²

,

Wurst

³

et al. 2020

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Propagation of homochirality plays a crucial role in the discussion on the origin of life. We investigated the role of structurally related enantiopure additives in chiral symmetry breaking during reactive crystallizations. We demonstrate that symmetry breaking can be driven towards the same absolute configuration as the additive if this additive forms an enantiospecific solid solution with the racemate. We observe two antagonistic processes: enantiospecific growth inhibition directs symmetry breaking to the opposite enantiomer following “the rule of reversal”, and enantiospecific solid solution formation that favors homochiral outcome. During continuous grinding, contributions of solid solution formation override contributions of enantiospecific growth inhibition, directing the process towards the absolute configuration of the additive. Collectively, our findings offer a potential mechanism for the propagation of homochirality.

show abstract

“…Enantiopure additives have been shown to direct the symmetry breaking in the Soai reaction to the same absolute configuration [3, 4, 5] . However, the mechanism of the Soai reaction is unique and its principles cannot be extended to prebiotic systems.…”

Section: Figurementioning

confidence: 99%

Enantiospecific Solid Solution Formation Triggers the Propagation of Homochirality

Baglai

¹

,

Leeman

²

,

Wurst

³

et al. 2020

View full text Add to dashboard Cite

Propagation of homochirality plays a crucial role in the discussion on the origin of life. We investigated the role of structurally related enantiopure additives in chiral symmetry breaking during reactive crystallizations. We demonstrate that symmetry breaking can be driven towards the same absolute configuration as the additive if this additive forms an enantiospecific solid solution with the racemate. We observe two antagonistic processes: enantiospecific growth inhibition directs symmetry breaking to the opposite enantiomer following “the rule of reversal”, and enantiospecific solid solution formation that favors homochiral outcome. During continuous grinding, contributions of solid solution formation override contributions of enantiospecific growth inhibition, directing the process towards the absolute configuration of the additive. Collectively, our findings offer a potential mechanism for the propagation of homochirality.

show abstract

Energy threshold for chiral symmetry breaking in molecular self-replication

Cited by 60 publications

References 46 publications

Absolute Autocatalytic Amplification under Heterogenous Phase Conditions Involving Subsequent Hydride Transfer and a Hemiacetal Intermediate

Absolute Autocatalytic Amplification under Heterogenous Phase Conditions Involving Subsequent Hydride Transfer and a Hemiacetal Intermediate

Enantiospecific Solid Solution Formation Triggers the Propagation of Homochirality

Enantiospecific Solid Solution Formation Triggers the Propagation of Homochirality

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