College of Chemistry and Chemical Engineering, Key Laboratory of Fuel Cell Technology of Guangdong Province, South China University of Technology, Guangzhou 510641, P. R. China.
Key Laboratory of Biomaterials of Guangdong Higher Education Institutes, Department of Biomedical Engineering, Jinan University, Guangzhou 510632, China.
Anal Chem. 2024 Mar 26;96(12):4809-4816. doi: 10.1021/acs.analchem.3c04820. Epub 2024 Mar 11.
As an effective ECL emitter, tetraphenylethene (TPE)-based molecules have recently been reported with aggregation-induced electrochemiluminescence (AIECL) property, while it is still a big challenge to control its aggregation states and obtain uniform aggregates with intense ECL emission. In this study, we develop three TPE derivatives carrying a pyridinium group, an alkyl chain, and a quaternary ammonium group via the Menschutkin reaction. The resulting molecules exhibit significantly red-shifted FL and enhanced ECL emissions due to the tunable reduction of the energy gap between the highest occupied molecular orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs). More importantly, the amphiphilicity of the as-developed molecules enables their spontaneous self-assembly into well-controlled spherical nanoaggregates, and the ECL intensity of nanoaggregates with 3 -CH- (named as C) is 17.0-fold higher compared to that of the original 4-(4-(1,2,2-triphenylvinyl)phenyl)pyridine (TPP) molecule. These cationic nanoaggregates demonstrate a high affinity toward bacteria, and an ECL sensor for the profiling of () was developed with a broad linear range and good selectivity in the presence of an -specific aptamer. This study provides an effective way to enhance the ECL emission of TPE molecules through their derivatization and a simple way to prepare well-controlled AIECL nanoaggregates for ECL application.
作为一种有效的 ECL 发射器,基于四苯乙烯(TPE)的分子最近被报道具有聚集诱导电化学发光(AIECL)特性,然而,控制其聚集状态并获得具有强烈 ECL 发射的均匀聚集物仍然是一个巨大的挑战。在这项研究中,我们通过曼尼希反应开发了三种带有吡啶鎓基团、烷基链和季铵基团的 TPE 衍生物。由于最高占据分子轨道(HOMO)和最低未占据分子轨道(LUMO)之间的能量间隙可调谐,所得分子表现出明显红移的 FL 和增强的 ECL 发射。更重要的是,所开发的分子的两亲性使其能够自发自组装成可控的球形纳米聚集体,并且具有 3 -CH-(命名为 C)的纳米聚集体的 ECL 强度比原始 4-(4-(1,2,2-三苯基乙烯基)苯基)吡啶(TPP)分子高 17.0 倍。这些阳离子纳米聚集体对细菌具有高亲和力,并在存在 -特异性适体的情况下,开发了一种用于 profiling 的 ECL 传感器,该传感器在宽线性范围内具有良好的选择性。这项研究为通过衍生化来增强 TPE 分子的 ECL 发射提供了一种有效方法,并为用于 ECL 应用的可控 AIECL 纳米聚集体的制备提供了一种简单方法。