We report the observation of spontaneous chiral symmetry breaking within ordered, racemic monolayers of theophylline, manifesting itself as extended, nanoscale unichiral stripes at the interface between molecular domains. Theophylline is a xanthine derivative playing an important role in several biochemical processes. Molecular chirality is induced by adsorption on the Au(111) surface, resulting in extended domains with two different racemic, ordered structures, coexisting with a disordered phase. By combining low-temperature scanning tunneling microscopy (LT-STM) and ab initio density functional theory calculations, we first provide a detailed picture of the interactions within the ordered assemblies, and we uncover the origin of the distinct contrast features in STM images. Secondly, experiments reveal the existence of nanoscale stripes of unichiral molecules separating racemic domains of one of the two ordered phases, giving rise to a local enantiomeric imbalance. Systematic theoretical investigation of their structure and chiral composition confirm their unichirality, with the specific handedness related to the registry between the two ordered domains facing the stripes. These findings can open the way to new insights into the elusive mechanisms leading to local chiral imbalances in racemic systems, possibly at the origin of biomolecular homochirality, as well as suggest novel approaches for stereoselective heterogeneous catalysis.

Spontaneous symmetry breaking on ordered, racemic monolayers of achiral theophylline: formation of unichiral stripes on Au(111)

PIVIDORI, MARCO;DRI, CARLO;BERTI, FEDERICO;PERESSI, MARIA;COMELLI, GIOVANNI
2016

Abstract

We report the observation of spontaneous chiral symmetry breaking within ordered, racemic monolayers of theophylline, manifesting itself as extended, nanoscale unichiral stripes at the interface between molecular domains. Theophylline is a xanthine derivative playing an important role in several biochemical processes. Molecular chirality is induced by adsorption on the Au(111) surface, resulting in extended domains with two different racemic, ordered structures, coexisting with a disordered phase. By combining low-temperature scanning tunneling microscopy (LT-STM) and ab initio density functional theory calculations, we first provide a detailed picture of the interactions within the ordered assemblies, and we uncover the origin of the distinct contrast features in STM images. Secondly, experiments reveal the existence of nanoscale stripes of unichiral molecules separating racemic domains of one of the two ordered phases, giving rise to a local enantiomeric imbalance. Systematic theoretical investigation of their structure and chiral composition confirm their unichirality, with the specific handedness related to the registry between the two ordered domains facing the stripes. These findings can open the way to new insights into the elusive mechanisms leading to local chiral imbalances in racemic systems, possibly at the origin of biomolecular homochirality, as well as suggest novel approaches for stereoselective heterogeneous catalysis.
http://pubs.rsc.org/en/Content/ArticleLanding/2016/NR/C6NR05301G
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11368/2891333
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