Highly enantioselective discrimination of amino acids using copper deposition on a gold electrode modified with homocysteine monolayer

Abstract

An extremely enhanced enantioselectivity was achieved for the detection of enantiomers of alanine (Ala), leucine (Leu), and 3,4-dihydroxyphenylalanine (DOPA) based on the voltammograms for the deposition of Cu from Cu complexes of the amino acids at an Au electrode modified with a self-assembled monolayer (SAM) of l-homocysteine (Hcy). The enantioselective current density peak for the Cu deposition was found to change with increasing number of potential cycles after the addition of Cu(II), and the highest enantioselectivity was observed immediately after the addition of Cu(II). Besides, enantioselectivity was not observed with proline, whose five-membered ring contains the nitrogen atom of a secondary amino group, while some amino acids with a primary amine group such as Ala, Leu, and DOPA exhibited enantioselectivity. These results suggest that the chiral ligand exchange reaction at the l-Hcy SAM-modified Au electrode, namely, the enantioselective formation of diastereomeric complexes of Cu(II) with target enantiomers and l-Hcy self-assembled on the Au electrode, plays an important role in the chiral discrimination based on the Cu deposition.