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To date, achieving enantioselective electroanalysis for electrochemically silent chiral molecules is still highly desired. Here, an ionic covalent organic framework (COF) consisting of the pyridinium cation was derived from the tripyridinium Zincke salt and 1,4-phenylenediamine in a one-pot reaction. The electrochemical measurements revealed that the ionic backbone contributed to the electron transfer with a low charge transfer resistance. Besides, the π-π + interaction between the pyridinium cation and ferrocenyl unit can promote the absorption of electroactive chiral ferrocenyl reagents into the hole of COF, so as to afford the electrochemical signals by themselves, replacing the testing enantiomers. As a result, the electroactive complex used as an electrochemical platform was highly effective at enantiomerically recognizing amino alcohols (prolinol, valinol, leucinol, and alaninol) and amino acids (methionine, serine, and penicillamine), giving the ratios of current intensity between l- and d-enantiomers in the range of 1.46-1.72. Moreover, the density functional theory calculations determined the possible intermolecular interactions between the testing enantiomers and chiral selector: namely, hydrogen bonds and electrostatic attractions. Overall, the present work offers an effective strategy to enlarge the electrochemical scope for chiral recognition based on electroactive chiral COFs.

Chiral analysis is of significant importance for living organisms since chirality is the fundamental phenomenon in nature. In this work, a bifunctional electrochemiluminescent (ECL) platform is constructed for chiral discrimination and chiral sensing. 3-Mercaptopropionic acid-functionalized CdSe quantum dots (CdSe QDs) are combined with aminated TiO 2 nanotubes (NH 2 -TiNTs) via amidation. The resultant CdSe QDs/TiNTs display significantly enhanced ECL signals due to the synergistic effect between CdSe QDs and TiNTs, which are then used for the chiral discrimination of the isomers of nine chiral amino acids (AAs) in the presence of d-AA oxidase (DAAO). DAAO can selectively catalyze the oxidation of d-AAs to generate H 2 O 2 , which acts as the coreaction reagent and triggers the ECL signals of CdSe QDs/TiNTs, and thus, the isomers of the nine chiral AAs can be effectively discriminated. In addition, the as-constructed ECL platform can also be used for the sensitive detection of d-AAs in the presence of DAAO with a wide linear range and a low limit of detection. These findings suggest that the CdSe QDs/TiNTs can work as a bifunctional ECL platform (chiral discrimination and chiral sensing), which might be an advanced ECL platform for biomedical applications.