Amplification of a Slight Enantiomeric Imbalance in Molecules Based on Asymmetric Autocatalysis:  The First Correlation between High Enantiomeric Enrichment in a Chiral Molecule and Circularly Polarized Light

Shibata, Takanori; Yamamoto, Jiro; Matsumoto, Naoko; Yonekubo, Shigeru; Osanai, Shunji; Soai, Kenso

doi:10.1021/ja980815w

Cited by 199 publications

(110 citation statements)

References 14 publications

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“…The product-initiator interaction was probed further by NMR spectroscopy, titrating each enantiomer of initiator 3 separately with increasing amounts of each enantiomer of product 2 in the presence of excess (iPr) 2 Zn. Product [2] [4] [4] and initiator alcohols rapidly form Zn alkoxides (2' and 3') in the presence of (iPr) 2 Zn. Probing with both 1 H and 2 H-NMR spectroscopy allows us to monitor changes in the initiator -OCH 3 and -OCD 3 groups simultaneously.…”

Section: Scheme 1 Soai Autocatalytic Reaction Initiated By An Isotopmentioning

confidence: 99%

“…While the chemistry of this singular reaction has little prebiotic significance in its own right, the reaction has inspired investigations aimed at understanding potential models for the origin of biological homochirality. 3 Since the original reports, Soai has gone on to demonstrate that the reaction may be initiated and directed with fidelity by a wide variety of physical and chemical chiral sources, including circularly polarized light, 4 quartz crystals, 5 and most strikingly, isotopically chiral molecules. [6][7][8][9] We report here the first mechanistic investigation probing the role of isotopically chiral initiators in selectively directing the Soai reaction of Scheme 1.…”

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confidence: 99%

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Elucidating the Role of Isotopically Chiral Initiators in the Soai Asymmetric Autocatalytic Reaction

Hawbaker¹,

Blackmond²

2018

Preprint

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A mechanistic rationalization is given for how asymmetric amplification is induced with fidelity in the Soai autocatalytic reaction by chiral initiators that are enantiomeric only by virtue of an isotope, e.g. -CH 3 vs. CD 3 . A transient inhibition of the autocatalytic pathway at the outset of the reaction implicates an interaction between initiator and product initially formed in the uncatalyzed background reaction. Selectivity in formation of the product-initiator complex ultimately induces a slight enantioenrichment in the active dimer catalysts that trigger and direct the autocatalytic pathway.

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Section: Scheme 1 Soai Autocatalytic Reaction Initiated By An Isotopmentioning

confidence: 99%

mentioning

confidence: 99%

Elucidating the Role of Isotopically Chiral Initiators in the Soai Asymmetric Autocatalytic Reaction

Hawbaker¹,

Blackmond²

2018

Preprint

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“…Therefore, cycles of partial polymerization and hydrolysis, evaporation and crystallization, as well as kinetic resolution have been proposed to increase the enantiomeric excess from very few percent towards homochirality (reviewed in [1]). Most promising seems to be the asymmetric amplification using enantioenriched auxiliaries with either catalytic [138] or autocatalytic function (Soai reaction type) [139][140][141].…”

Section: Criticismmentioning

confidence: 99%

Photochirogenesis: Photochemical Models on the Origin of Biomolecular Homochirality

et al. 2010

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Current research focuses on a better understanding of the origin of biomolecular asymmetry by the identification and detection of the possibly first chiral molecules that were involved in the appearance and evolution of life on Earth. We have reasons to assume that these molecules were specific chiral amino acids. Chiral amino acids have been identified in both chondritic meteorites and simulated interstellar ices. Present research reasons that circularly polarized electromagnetic radiation was identified in interstellar environments and an asymmetric interstellar photon-molecule interaction might have triggered biomolecular symmetry breaking. We review on the possible prebiotic interaction of 'chiral photons' in the form of circularly polarized light, with early chiral organic molecules. We will highlight recent studies on enantioselective photolysis of racemic amino acids by circularly polarized light and experiments on the asymmetric OPEN ACCESS Symmetry 2010, 2 1056 photochemical synthesis of amino acids from only one C and one N containing molecules by simulating interstellar environments. Both approaches are based on circular dichroic transitions of amino acids that will be presented as well.

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“…Kenso Soai and his team (Shibata et al, 1998) have demonstrated the autocatalytic bifurcation framework as well. They took a mixture of compounds containing a small excess of one enantiomer of the amino acid leucine.…”

Section: Chirality Bifurcationmentioning

confidence: 99%

Cosmic Symmetry-breaking, Bifurcation, Fractality and Biogenesis

King¹

2007

Neuroquantology

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This paper explores the non-linear quantum foundations of biogenesis in interactive bifurcations between the properties of the elements, sourced in the transitions induced by cosmic symmetry-breaking. The key interactions forming the biogenic pathway are modeled in terms of interactive quantum bifurcations explaining why the bioelements play the interactive role they do and why central biomolecules are cosmologically abundant products of the gas clouds forming young stars. RNA and related nucleotide molecules gain a plausible cosmic status, along with major features of the genetic code, and key features of metabolism, including ion and electron transport, the citric acid cycle and glycolysis.Key Words: cosmology, symmetry-breaking, molecular evolution, chaos, bifurcation, complex system, fractal, biogenesis, astrobiology I IntroductionThe thesis of this paper is that biological structures such as tissues, and organisms are cosmological structures, culminating the interactive phase of symmetry-breaking, as fundamental as stars and galaxies to the cosmic design. This process is described in detail in this paper as a fundamental manifestation of nonlinear quantum science, elaborating the fractal nature of fundamental force interaction, inevitable from the twisted nature of the forces, as they have emerged in our Universe. Symmetry-breaking as elucidated firstly in terms of the weak and electromagnetic forces, fig 5(a) results from evolution of the Universe from a symmetrical state to one in which the Higgs field has become polarized into a state of lower energy, similar to that of a ferromagnetic substance. It is the transition of this underlying parameter that is responsible for the bifurcations we shall consider.Although life is of fragile insignificance among the immensity of cosmic energies, its tiny entropy-reducing photosynthetic energy budget and fragile chemical bonds overwhelmed on the cosmic scale, it is nevertheless the interactive consummation of all the forces of nature acting together in sequence. Biological evolution is a stochastic 2 process combining random mutation and selective advantage, many of whose manifestations are opportunistic, but others the inevitable result of selective forces and environmental bifurcations. Although biological structures are genetically coded in a vast variety of ways by specific nucleic acid sequences, many features of life, 1 Mathematics Department, University of Auckland, New Zealand, E-mail: c.king@auckland.ac.nz 2 Stochastic -a process mediated partly by random factors, such as the drunkard's walk of Brownian motion.

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Amplification of a Slight Enantiomeric Imbalance in Molecules Based on Asymmetric Autocatalysis: The First Correlation between High Enantiomeric Enrichment in a Chiral Molecule and Circularly Polarized Light

Cited by 199 publications

References 14 publications

Elucidating the Role of Isotopically Chiral Initiators in the Soai Asymmetric Autocatalytic Reaction

Elucidating the Role of Isotopically Chiral Initiators in the Soai Asymmetric Autocatalytic Reaction

Photochirogenesis: Photochemical Models on the Origin of Biomolecular Homochirality

Cosmic Symmetry-breaking, Bifurcation, Fractality and Biogenesis

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