高娟娟博士研究生与团队成员，朱伟青，林雪珍，马闯等通过在低温水热过程中分层自组装环糊精和N,N-二甲基-4-（苯基乙炔基）苯胺（MPEA）到氮掺杂石墨烯上，成功构建了电化学活性传感纳米材料CD-MPEA-NG。通过利用傅里叶变换红外光谱、X射线衍射仪和差分脉冲伏安法等，证实了高性能CD-MPEA-NG的独特纳米结构。特别地，利用密度泛函理论（DFT-D）用于优化和描述NG和MPEA异源二聚体的面对面包装结构。 CD-MPEA-NG传感器对二羟基苯异构体表现出高度灵敏的性能，而不依赖昂贵的贵金属或复杂的制备工艺。实验结果表明，在NG和MPEA作为耦合传感平台以及CD作为超分子腔的协同作用下可以显着提高电化学响应。邻、间、对苯二酚的检测限（3倍信噪比）分别为0.008,0.018和0.011 μmol/L。此外，CD-MPEA-NG传感器显示出极好的抗干扰性、重现性和稳定性，并且在应用于南京河水中检测异构体方面有着令人满意的回收率。令人鼓舞的性能和简化的制备方法强有力地支持了CD-MPEA-NG传感器是一个非常有吸引力的电极，可以作为无缺陷和灵敏的电分析技术进行开发。

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

Authors: Juanjuan Gao , Jingkun Fang , Xuehai Ju , Weiqing Zhu, Xuezhen Lin , Shupeng Zhang ^*,, Chuang Ma , Haiou Song ^*

Abstract: 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 the Fourier transform infrared spectra, an X-ray diffractometer, a 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 towards dihydroxybenzene isomers, without relying on expensive noble metal or 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 a seamless and sensitive electroanalytical technique.

 
全文链接：http://pubs.acs.org/doi/10.1021/acsami.7b12463

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