Perylene-functionalized graphene sheets modified with β-cyclodextrin for the voltammetric discrimination of phenylalanine enantiomers

Abstract

A facile approach was reported to synthesize β-cyclodextrin functionalized graphene that is bridged by 3,4,9,10-perylene tetracarboxylic acid (rGO-PTCA-CD) via a chemical route that involves the functionalization of rGO with PTCA followed by covalently cross-linking NH2-β-CD. The as-prepared rGO-PTCA-CD was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and electrochemical methods. The working electrodes were thoroughly studied for the cyclic voltammetry by using [Fe(CN)6]4−/3- as redox probe and using ferrocene as an internal standard. Furthermore, rGO-PTCA-CD was successfully applied to the recognition of phenylalanine enantiomers. The host-guest inclusion interaction between rGO-PTCA-CD and the phenylalanine enantiomers was investigated by differential pulse voltammetry with Fc used as a competitor. The recognition result showed that the rGO-PTCA-CD-modified glassy carbon electrode exhibited higher chiral recognition capability for L-Phe than for D-Phe with an enantioselectivity coefficient of 2.07. The proposed modified electrode had a limit of detection of 0.08 nM and 0.2 nM (S/N = 3) for L-Phe and D-Phe, respectively, with a linear response range of 0.01 mM to 5 mM, which was ascribed to the synergy of the rGO-PTCA (e.g., its excellent electrochemical performance) and β-CD (e.g., the hydrophobic inner cavity with good molecular recognition and enrichment abilities).