Hierarchical Self-Assembly of Cyclodextrin and Dimethylamino-Substituted Arylene-Ethynylene on N-doped Graphene for Synergistically Enhanced Electrochemical Sensing of Dihydroxybenzene Isomers.

An electrochemically active sensing nanomaterial (denoted as CD-MPEA-NG) has been successfully constructed by an hierarchical self-assembly of cyclodextrin (CD) and N,N-dimethyl-4-(phenylethynyl)aniline (MPEA) on N-doped graphene (NG) in a low-temperature hydrothermal process. The unique nanostructure of the high-performance CD-MPEA-NG was confirmed by utilizing Fourier transform infrared spectra, an X-ray diffractometer, and differential pulse voltammetry (DPV), etc. In particular, the method of density functional theory with dispersion energy (DFT-D) of wB97XD/LanL2DZ was employed to optimize and describe the face-to-face packing structure of heterodimers of NG and MPEA. The CD-MPEA-NG sensor exhibits highly sensitive performance toward dihydroxybenzene isomers, without relying on expensive noble metal or a complicated preparation process. The experimental results demonstrate that given the synergistic effect of NG and MPEA as a coupled sensing platform, CD as a supramolecular cavity can significantly enhance the electrochemical response. The detection limits (S/N = 3) for catechol (CT), resorcinol (RS), and hydroquinone (HQ) are 0.008, 0.018, and 0.011 μM by DPV, respectively. Besides, the CD-MPEA-NG sensor shows a superb anti-interference, reproducibility, and stability, and satisfactory recovery aimed at detecting isomers in Nanjing River water. The encouraging performance as well as simplified preparation approach strongly support the CD-MPEA-NG sensor is a fascinating electrode to develop as a seamless and sensitive electroanalytical technique.