From parity to chirality: chemical implications revisited

Авалос, M.; Babiano, Reyes; Cintas, Pedro; Jiménez, José L.; Palacios, Juan C.

doi:10.1016/s0957-4166(00)00265-2

Cited by 158 publications

(61 citation statements)

References 198 publications

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“…According to [8], k 0 must be kept sufficiently small. Otherwise, these chirally unspecific reactions would proceed too rapidly thus generating large amounts of racemic matter that swamps the amplification process driven by the autocatalytic (1) and mutual inhibition steps (2). To take this important observation into account, we simply set k 0 = 0 from the outset.…”

Section: Introductionmentioning

confidence: 99%

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Reaction-noise induced homochirality

Hochberg

Zorzano

2006

Chemical Physics Letters

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Starting from the chemical master equation, we employ field theoretic techniques to derive Langevin-type equations that exactly describe the stochastic dynamics of the Frank chiral amplification model with spatial diffusion. The intrinsic multiplicative noise properties are completely and rigorously derived by this procedure. We carry out numerical simulations in two spatial dimensions. When the inherent spatio-temporal fluctuations are properly included, then complete chiral amplification results from a purely racemic initial configuration. Phase separation can also arise in which the enantiomers coexist in spatially segregated domains separated by a sharp racemic interface or boundary.

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Section: Introductionmentioning

confidence: 99%

“…Mirror symmetry is broken in the bioorganic world and life as we know it is invariably linked with homochirality. For recent reviews that survey existing hypotheses concerning this phenomenon, specific experimental realizations and additional references, see [1,2,3].…”

Section: Introductionmentioning

confidence: 99%

Reaction-noise induced homochirality

Hochberg

Zorzano

2006

Chemical Physics Letters

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“…There has been speculation that this minute difference could still be large enough to trigger the observed homochirality in living organisms, the biochemistry showing, with very few exceptions, a distinct preference for L-amino acids and D-monosaccharides over their mirror images. The role of weak interaction in the origin of homochiral life is still a subject of debate [4][5][6][7][8][9][10] , which is one motivation for an experimental observation of parity violation (PV) in molecules that would enable to address this question quantitatively.…”

Section: Introduction: Context and Historymentioning

confidence: 99%

High resolution spectroscopy of methyltrioxorhenium: towards the observation of parity violation in chiral molecules

Stoeffler

Darquié

Shelkovnikov

et al. 2011

Phys. Chem. Chem. Phys.

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Originating from the weak interaction, parity violation in chiral molecules has been considered as a possible origin of the biohomochirality. It was predicted in 1974 but has never been observed so far. Parity violation should lead to a very tiny frequency difference in the rovibrational spectra of the enantiomers of a chiral molecule. We have proposed to observe this predicted frequency difference using the two photon Ramsey fringes technique on a supersonic beam. Promising candidates for this experiment are chiral oxorhenium complexes, which present a large effect, can be synthesized in large quantity and enantiopure form, and can be seeded in a molecular beam. As a first step towards our objective, a detailed spectroscopic study of methyltrioxorhenium (MTO) has been undertaken. It is an ideal test molecule as the achiral parent molecule of chiral candidates for the parity violation experiment. For the 187 Re MTO isotopologue, a combined analysis of Fourier transform microwave and infrared spectra as well as ultra-high resolution CO 2 laser absorption spectra enabled the assignment of 28 rotational lines and 71 rovibrational lines, some of them with a resolved hyperfine structure. A set of spectroscopic parameters in the ground and first excited state, including hyperfine structure constants, was obtained for the ν as antisymmetric Re=O stretching mode of this molecule. This result validates the experimental approach to be followed once a chiral derivative of MTO will be synthesized, and shows the benefit of the combination of several spectroscopic techniques in different spectral regions, with different set-ups and resolutions. First high resolution spectra of jet-cooled MTO, obtained on the setup being developed for the observation of molecular parity violation, are shown, which constitutes a major step towards the targeted objective. † Supplementary information available in the ancillary file: Measured and fitted transition frequencies as well as spectroscopic constants.1

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“…However, modern theoretical studies [11][12][13][14][15][16][17][18][19][20][21][22][23]26,28,30,31,33,[36][37][38][39][40][41]43,44,46] have claimed that an image and its mirror molecule are no longer enantiomers due to an energy inequality induced by the existence of PV-WNC. Due to a parity-violating energy shift (PVES) of the electronic binding energy with a positive value, +E PV , for the image molecule and a PVES with a negative value, -E PV , for the mirror image molecule, or vice versa, PVES makes the pair become a diastereomer, exhibiting subtle differences in physical properties and chemical processes.…”

Section: Introductionmentioning

confidence: 99%

Mirror Symmetry Breaking in Helical Polysilanes: Preference between Left and Right of Chemical and Physical Origin

Fujiki

2010

Symmetry

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Abstract:From elemental particles to human beings, matter is dissymmetric with respect to mirror symmetry. In 1860, Pasteur conjectured that biomolecular handednesshomochirality-may originate from certain inherent dissymmetric forces existing in the universe. Kipping, a pioneer of organosilicon chemistry, was interested in the handedness of sodium chlorate during his early research life. Since Kipping first synthesized several Si-Si bonded oligomers bearing phenyl groups, Si-Si bonded high polymers carrying various organic groups-polysilanes-can be prepared by sodium-mediated condensation of the corresponding organodichlorosilanes. Among these polysilanes, optically active helical polysilanes with enantiomeric pairs of organic side groups may be used for testing the mirror symmetry-breaking hypothesis by weak neutral current (WNC) origin in the realm of chemistry and material science. Several theoretical studies have predicted that WNC-existing chiral molecules with stereogenic centers and/or stereogenic bonds allow for distinguishing between image and mirror image molecules. Based on several amplification mechanisms, theorists claimed that minute differences, though still very subtle, may be detectable by precise spectroscopic and physicochemical measurements if proper chiral molecular pairs were employed. The present paper reports comprehensively an inequality between six pairs of helical polysilane high polymers, presumably, detectable by (chir)optical and achiral 29 Si-/ 13 C-NMR spectra, and viscometric measurements.

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From parity to chirality: chemical implications revisited

Cited by 158 publications

References 198 publications

Reaction-noise induced homochirality

Reaction-noise induced homochirality

High resolution spectroscopy of methyltrioxorhenium: towards the observation of parity violation in chiral molecules

Mirror Symmetry Breaking in Helical Polysilanes: Preference between Left and Right of Chemical and Physical Origin

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