Chiral molecular imprinted sensor for highly selective determination of D-carnitine in enantiomers via dsDNA-assisted conformation immobilization

Abstract

In this paper, a novel approach was established on the basis of a molecularly imprinted technique with the aid of double-stranded deoxyribonucleic acid (dsDNA) embedded in a molecularly imprinted polymer (MIP) membrane as a new functional unit with chiral recognition for highly specific chiral recognition. The chiral molecules were immobilized and anchored in the cavities of the MIP membrane on the basis of the three-dimensional structure of a molecule determined by the functional groups, spatial characterization of the cavities of MIPs, and the spatial orientation with dsDNA embedded in MIPs. D-carnitine was selected as an example of a chiral molecular template, which intercalated into dsDNA immobilized on the gold electrode surface to form dsDNA-D-carnitine complex, and then the complex was embedded in the MIP during electropolymerization. After elution, the stereo-selective cavities were obtained. Our findings have shown that AAAA-TTTT base sequence had high affinity for D-carnitine intercalation. Combined with the electrochemical detection method, MIP sensor was prepared. The selectivity of the MIP sensor to ultratrace D-carnitine was significantly improved; the sensor had remarkable stereo-selectivity and highly chiral specific recognition to D-carnitine, and L-carnitine with a concentration of 10,000 times D-carnitine did not interfere with the detection of D-carnitine in the assay of raceme. The sensor also exhibited high sensitivity to ultratrace D-carnitine determination with a linear response to the concentration of D-carnitine in the range of 3.0 × 10−16 mol/L to 4.0 × 10−13 mol/L, with a detection limit of 2.24 × 10−16 mol/L. The mechanism of chiral recognition was studied, and result showed that apart from the recognition effect of imprinted cavities, dsDNA provided chiral selectivity to the spatial orientation of chiral molecules via the intercalation of chiral molecules with dsDNA and electrostatic interaction with groups of DNA base.