Chiral Selective Chemistry Induced by Natural Selection of Spin-Polarized Electrons

The search to understand the origin of homochirality in nature has been ongoing since the time of Pasteur. Previous work has shown that DNA can act as a spin filter for low‐energy electrons and that spin‐polarized secondary electrons produced by X‐ray irradiation of a magnetic substrate can induce c...

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Veröffentlicht in:Angewandte Chemie (International ed.) 2015-06, Vol.54 (25), p.7295-7298
Hauptverfasser: Rosenberg, Richard A., Mishra, Debabrata, Naaman, Ron
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Sprache:eng
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Zusammenfassung:The search to understand the origin of homochirality in nature has been ongoing since the time of Pasteur. Previous work has shown that DNA can act as a spin filter for low‐energy electrons and that spin‐polarized secondary electrons produced by X‐ray irradiation of a magnetic substrate can induce chiral selective chemistry. In the present work it is demonstrated that secondary electrons from a substrate that are transmitted through a chiral overlayer cause enantiomeric selective chemistry in an adsorbed adlayer. We determine the quantum yields (QYs) for dissociation of (R)‐ or (S)‐epichlorohydrin adsorbed on a chiral self‐assembled layer of DNA on gold and on bare gold (for control). The results show that there is a significant difference in the QYs between the two enantiomers when adsorbed on DNA, but none when they are adsorbed on bare Au. We propose that the effect results from natural spin filtering effects cause by the chiral monolayer. Secondary electrons from a substrate are transmitted through a chiral overlayer, causing enantiomeric selectivity in an adsorbed adlayer. Quantum yields (QYs) are determined for dissociation of (R)‐ or (S)‐epichlorohydrin adsorbed on a chiral self‐assembled layer of DNA on gold and on bare gold (for control). The QYs differ significantly between the two enantiomers when adsorbed on DNA, but not when they are adsorbed on bare Au.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201501678