Molecular Origins of Chiral Amplification on an Achiral Surface: 2D Monolayers of Aspartic Acid on Cu(111).
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 36877997.
- Also identified by DOI 10.1021/acsnano.2c12312 and PMC identifier 10062026.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Recent experiments have demonstrated an intriguing phenomenon in which adsorption of a nonracemic mixture of aspartic acid (Asp) enantiomers onto an achiral Cu(111) metal surface leads to autoamplification of surface enantiomeric excess, <i>ee</i><sub>s</sub>, to values well above those of the impinging gas mixtures, <i>ee</i><sub>g</sub>. This is particularly interesting because it demonstrates that a slightly nonracemic mixture of enantiomers can be further purified simply by adsorption onto an achiral surface. In this work, we seek a deeper understanding of this phenomena and apply scanning tunneling microscopy to image the overlayer structures formed by mixed monolayers of d- and l-Asp on Cu(111) over the full range of surface enantiomeric excess; <i>ee</i><sub>s</sub> = -1 (pure l-Asp) through <i>ee</i><sub>s</sub> = 0 (racemic dl-Asp) to <i>ee</i><sub>s</sub> = 1 (pure d-Asp). Both enantiomers of three chiral monolayer structures are observed. One is a conglomerate (enantiomerically pure), another is a racemate (equimolar mixture of d- and l-Asp); however, the third structure accommodates both enantiomers in a 2:1 ratio. Such solid phases of enantiomer mixtures with nonracemic composition are rare in 3D crystals of enantiomers. We argue that, in 2D, the formation of chiral defects in a lattice of one enantiomer is easier than in 3D, simply because the stress associated with the chiral defect in a 2D monolayer of the opposite enantiomer can be dissipated by strain into the space above the surface.