An electrochemical and computational study for discrimination of D- and L-cystine by reduced graphene oxide/beta-cyclodextrin

Here, we report a novel enantioselective electrochemical biosensor for the discrimination of cystine enantiomers (D- and L-cystine) using a chiral interface for the specific recognition of D- and L-cystine. The biosensor is based on reduced graphene oxide modified by beta-cyclodextrin (rGO/beta-CD) at the GCE surface. During the preparation of rGO/beta-CD/GCE, the modified electrode surfaces were characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The electrochemical behaviours of the D- and L-cystine were investigated using the rGO/beta-CD/GCE by CV and compared to bare GCE. A clear separation between the oxidation peak potentials of D- and L-cystine was observed at 1.32 and 1.42 V, respectively. The electrochemical discrimination performance of the fabricated chiral sensor was also examined by differential pulse voltammetry (DPV) in a mixed solution of D- and L-cystine. In addition, the DPV technique was used for the determination of D- and L-cystine at low concentration values in the range of 1.0-10.0 mM. To investigate the amperometric response of rGO/beta-CD/GCE towards D- and L-cystine, the chronoamperometry technique was used in the concentration range of 10.0-100.0 mu M. The interactions of the enantiomers with rGO/beta-CD were modelled by molecular docking using AutoDock Vina, and the interaction energies were predicted to be -4.8 and -5.3 kcal mol(-1) for D- and L-cystine, respectively. The corresponding values of binding constants were calculated to be 3.32 x 10(3) and 7.71 x 10(3) M-1, respectively. The experimental and molecular docking results indicate that the rGO/beta-CD/GCE has a different affinity for each enantiomer.