Highly Efficient Aggregation-Induced Enhanced Electrochemiluminescence of Cyanophenyl-Functionalized...

Exploring new electrochemiluminescence (ECL) luminophores with high ECL efficiency and good stability in aqueous solution is in great demand for biological sensing. In this work, highly efficient aggregation-induced enhanced ECL of cyanophenyl-functionalized tetraphenylethene (tetra[4-(4-cyanophenyl)phenyl]ethene, TCPPE) and its application in biothiols analysis were reported. TCPPE contains four 4-cyanophenyl groups covalently attached to the tetraphenylethene (TPE) core, generating a nonplanar three-dimensional twisted conformation structure. TCPPE nanoparticles (NPs) with an average size of 15.84 nm were prepared by a precipitation method. High ECL efficiency (593%, CdS as standard) and stable ECL emission (over one month) were obtained for TCPPE NPs in aqueous solution. The unique properties of TCPPE NPs could be ascribed to the efficient suppression of nonradiative transition, the decrease of the energy gap, and the increase of anionic radical stability, which were proved by theoretical calculation and electrochemical and fluorescence methods. Contrasting aggregation-induced ECL chromic emission was first observed for TCPPE NPs. As a proof-of-methodology, an ECL method was developed for three biothiol assays with detection limits of 6, 7, and 300 nM for cysteine, homocysteine, and glutathione, respectively. This work demonstrates that TCPPE NPs are promising ECL luminophores, and the incorporation of appropriate substituents into luminophores can improve ECL efficiency and radical stability.