Wang Xiaofei, Liu Huiwen, Jiang Jiaxing, Qian Manping, Qi Honglan, Gao Qiang, Zhang Chengxiao
Key Laboratory of Analytical Chemistry for Life Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an, 710062, People's Republic of China.
Key Laboratory for Macromolecular Science of Shaanxi Province, School of Materials Science and Engineering, Shaanxi Normal University, Xi'an, 710062, People's Republic of China.
Anal Chem. 2022 Apr 5;94(13):5441-5449. doi: 10.1021/acs.analchem.2c00631. Epub 2022 Mar 21.
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.
探索具有高电化学发光（ECL）效率且在水溶液中具有良好稳定性的新型ECL发光体对生物传感具有迫切需求。在这项工作中，报道了氰基苯基官能化的四苯乙烯（四[4-(4-氰基苯基)phenyl]乙烯，TCPPE）的高效聚集诱导增强ECL及其在生物硫醇分析中的应用。TCPPE包含四个与四苯乙烯（TPE）核心共价连接的4-氰基苯基，产生非平面三维扭曲构象结构。通过沉淀法制备了平均尺寸为15.84 nm的TCPPE纳米颗粒（NPs）。TCPPE NPs在水溶液中获得了高ECL效率（以CdS为标准，为593%）和稳定的ECL发射（超过一个月）。TCPPE NPs的独特性质可归因于对非辐射跃迁的有效抑制、能隙的减小以及阴离子自由基稳定性的增加，这通过理论计算以及电化学和荧光方法得到了证明。首次观察到TCPPE NPs的聚集诱导ECL变色发射。作为方法验证，开发了一种ECL方法用于三种生物硫醇分析，对半胱氨酸、同型半胱氨酸和谷胱甘肽的检测限分别为6、7和300 nM。这项工作表明TCPPE NPs是有前景的ECL发光体，并且在发光体中引入适当的取代基可以提高ECL效率和自由基稳定性。
