Symmetry arguments in chemistry

Dunitz, Jack D.

doi:10.1073/pnas.93.25.14260

Cited by 37 publications

(35 citation statements)

References 18 publications

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“…We also note that in the absence of a specific chiral bias, the net enantiomeric excess in the APED model, and in many models of chiral symmetry breaking, is random and may be attributable to amplification of stochastic fluctuations about the initial near-racemic state [17] due to environmental influences [27] which may or may not induce turbulence [8]. Therefore, as shown in Figure 4, isolated regions can develop opposite chirality.…”

Section: Discussionmentioning

confidence: 99%

Toward Homochiral Protocells in Noncatalytic Peptide Systems

Gleiser

Walker

2009

Orig Life Evol Biosph

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The activation-polymerization-epimerization-depolymerization (APED) model of Plasson et al. has recently been proposed as a mechanism for the evolution of homochirality on prebiotic Earth. The dynamics of the APED model in two-dimensional spatially-extended systems is investigated for various realistic reaction parameters. It is found that the APED system allows for the formation of isolated homochiral proto-domains surrounded by a racemate. A diffusive slowdown of the APED network induced, for example, through tidal motion or evaporating pools and lagoons leads to the stabilization of homochiral bounded structures as expected in the first self-assembled protocells.

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Section: Discussionmentioning

confidence: 99%

Toward Homochiral Protocells in Noncatalytic Peptide Systems

Gleiser

Walker

2009

Orig Life Evol Biosph

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“…A much-debated question is whether the observed homochirality of biomolecules is a prerequisite for life's emergence or if it developed as its consequence [37,38]. Adding to the mystery, prebiotically relevant laboratory syntheses yield racemic mixtures [39]. This is especially surprising given that statistical fluctuations of reactants will invariably bias one enantiomer over the other [40]: every synthesis is ab initio asymmetric.…”

Section: Deciphering the Origin Of Life's Chiralitymentioning

confidence: 99%

Life's chirality from prebiotic environments

Gleiser

Walker

2012

International Journal of Astrobiology

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A key open question in the study of life is the origin of biomolecular homochirality: almost every life-form on Earth has exclusively levorotary amino acids and dextrorotary sugars. Will the same handedness be preferred if life is found elsewhere? We review some of the pertinent literature and discuss recent results suggesting that life's homochirality resulted from sequential chiral symmetry breaking triggered by environmental events. In one scenario, autocatalytic prebiotic reactions undergo stochastic fluctuations due to environmental disturbances. In another, chiral-selective polymerization reaction rates influenced by environmental effects lead to substantial chiral excess even in the absence of autocatalysis. Applying these arguments to other potentially life-bearing platforms has implications to the search for extraterrestrial life: we predict that a statistically representative sampling of extraterrestrial stereochemistry will be racemic (chirally neutral) on average.

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“…With X‐ray crystallography, “structural chemistry” became the “study of the metrical aspects of atomic arrangements in molecules,” Jack's definition with Hans‐Beat Bürgi. Before the diffraction era, structural chemistry was grounded in qualitative symmetry arguments, the first of which followed from Pasteur's 1848 insight into the organization of atoms in tartrate salts. By separating enantiomorphous crystals of the sodium ammonium tartrate conglomerate and subsequently dissolving the subsets of crystals, Pasteur linked macroscopic chirality, the shapes of material objects, with microscopic chirality, required by the action of invisible molecules on plane‐polarized light ,.…”

Section: Pasteurmentioning

confidence: 99%

Seeing Molecular Configuration in Twisted Crystal Form

Kahr

Shtukenberg

2016

Israel Journal of Chemistry

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Structural chemistry began with Louis Pasteur, who first saw the configuration of molecules manifest in the shapes of crystals. Here is reviewed forgotten, century‐old efforts to make molecular configuration vivid in polycrystalline ensembles. Resorcinol, and a variety of other simple molecular crystals, when grown from the melt in the presence of resolved chiral additives, such as tartaric acids, form spectacular bull's‐eye patterns evident in the petrographic microscope. Concentric, rhythmic optical bands in so‐called banded spherulites are tell‐tale signs of the twisting of helicoidal crystalline lamellae. The sense of twisting was assayed by correlating displacements of extinction bands on rotation with additive configurations. Thus, the arrangements of atoms in space were made manifest in crystal form – not in the appearance of hemihedral facets, but rather, in the chirality of nonclassical morphologies with Gaussian curvature. The far reaching consequences of these experiments for molecular crystal growth and form, long ago foreseen, are evaluated with the hindsight of an extra century of experience and sophistication. The narrative aims to draw a continuous thread through the work of Pasteur, Grigorii Vyroubov, Frédéric Wallerant, John Monteath Robertson, Hélène Metzger, and Jack Dunitz.

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Symmetry arguments in chemistry

Cited by 37 publications

References 18 publications

Toward Homochiral Protocells in Noncatalytic Peptide Systems

Toward Homochiral Protocells in Noncatalytic Peptide Systems

Life's chirality from prebiotic environments

Seeing Molecular Configuration in Twisted Crystal Form

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