Significant Chiral Asymmetry Observed in Neutral Amino Acid Ultraviolet Photolysis

The origin of homochirality in biological organisms remains an open question. Some suggest that its origin might be extraterrestrial, specifically due to the exposure of chiral molecules to circularly polarized photons in interstellar space, which could cause an initial population imbalance leading to the homochirality observed today. However, this extraterrestrial hypothesis has not been widely accepted, largely due to the belief that molecular optical rotatory dispersion is too insignificant to create the substantial imbalance required for homochirality. Here we report experimental evidence that specific conformers of neutral amino acids exhibit significant asymmetry in the chiral destroying dissociation rate induced by circularly polarized photons. The observed anisotropy factor for the lowest energy conformer of leucine was remarkably large, reaching 0.1─a factor of 13 times larger than observed for zwitterionic leucine in solid films, and nearly 40 times greater than the anisotropy reported in the electronic absorption spectrum of gas-phase leucine ensembles at room temperature. This significant finding indicates that even if reported anisotropy values in the electronic absorption spectrum are low, the dissociation asymmetry of certain conformers can still be substantial. An anisotropy factor of 0.1 could result in an initial enantiomeric excess exceeding 10%, even with a 90% extent of reaction. This discovery suggests that asymmetric photodissociation of amino acids may have been a crucial factor in the emergence of biological homochirality.

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Journal
Journal of the American Chemical Society
Published
2024-11-07
DOI
https://doi.org/10.1021/jacs.4c07585
Primary Topic
Origins and Evolution of Life
Type
article
Field-Weighted Citation Impact
0.00

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article

Significant Chiral Asymmetry Observed in Neutral Amino Acid Ultraviolet Photolysis

L. Zeng, Takamasa Momose, Pavle Djuricanin, Kirk W. Madison et al.
Journal of the American Chemical Society
Origins and Evolution of Life
article

Significant Chiral Asymmetry Observed in Neutral Amino Acid Ultraviolet Photolysis

L. Zeng, Takamasa Momose, Pavle Djuricanin, Kirk W. Madison, Ilsa R. Cooke, Brendan Moore
article en

Abstract

The origin of homochirality in biological organisms remains an open question. Some suggest that its origin might be extraterrestrial, specifically due to the exposure of chiral molecules to circularly polarized photons in interstellar space, which could cause an initial population imbalance leading to the homochirality observed today. However, this extraterrestrial hypothesis has not been widely accepted, largely due to the belief that molecular optical rotatory dispersion is too insignificant to create the substantial imbalance required for homochirality. Here we report experimental evidence that specific conformers of neutral amino acids exhibit significant asymmetry in the chiral destroying dissociation rate induced by circularly polarized photons. The observed anisotropy factor for the lowest energy conformer of leucine was remarkably large, reaching 0.1─a factor of 13 times larger than observed for zwitterionic leucine in solid films, and nearly 40 times greater than the anisotropy reported in the electronic absorption spectrum of gas-phase leucine ensembles at room temperature. This significant finding indicates that even if reported anisotropy values in the electronic absorption spectrum are low, the dissociation asymmetry of certain conformers can still be substantial. An anisotropy factor of 0.1 could result in an initial enantiomeric excess exceeding 10%, even with a 90% extent of reaction. This discovery suggests that asymmetric photodissociation of amino acids may have been a crucial factor in the emergence of biological homochirality.

Journal of the American Chemical SocietyVol. 146(50)
TRIUMF (CA), University of British Columbia (CA)
Canada Foundation for Innovation, Deutsche Forschungsgemeinschaft, Natural Sciences and Engineering Research Council of Canada
Openalex Percentile: Top 86%
Origins and Evolution of Life
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