Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering , Southwest University , Chongqing 400715 , People's Republic of China.
Anal Chem. 2019 Mar 5;91(5):3710-3716. doi: 10.1021/acs.analchem.8b05949. Epub 2019 Feb 15.
Apart from the reported energy transfer mechanism of aggregation-induced electrochemiluminescence (AI-ECL) enhancement, a new strategy named restriction of intramolecular motions-driven ECL (RIM-ECL) enhancement is first proposed based on the phenomenon of a very strong electrochemiluminescence observed on the hexagonal tetraphenylethylene microcrystals (TPE MCs) in aqueous solution. Compared to TPE in molecule-isolation state with faint ECL, TPE in aggregate state (TPE MCs) showed a significantly enhanced ECL that was due to the restriction of intramolecular motions (RIM). Inspired by the unique luminescence characteristic of TPE MCs, we integrated the novel ECL emitter of TPE MCs and target-activated bipedal DNA walker together to fabricate a sensitive "off-on" ECL biosensor for Mucin 1 (MUC1) assay, which exhibited desirable linear response for a concentration scope from 1 fg/mL to 1 ng/mL with a low detection limit of 0.29 fg/mL. The RIM enhanced ECL demonstrated by the TPE MCs provides a new chapter in the exploration of aggregated organic emitters for further applications.
除了已报道的聚集诱导电化学发光（AI-ECL）增强的能量转移机制外，我们基于在水溶液中观察到的六方四苯乙烯微晶体（TPE MCs）上非常强的电化学发光现象，首次提出了一种新的策略，称为限制分子内运动驱动的电化学发光（RIM-ECL）增强。与分子隔离状态下发光微弱的 TPE 相比，聚集态的 TPE（TPE MCs）显示出显著增强的电化学发光，这是由于分子内运动受到限制（RIM）。受 TPE MCs 独特发光特性的启发，我们将新型电化学发光发射器 TPE MCs 和靶标激活的双足 DNA walker 集成在一起，用于构建用于 Mucin 1（MUC1）检测的灵敏“关-开”电化学发光生物传感器，该传感器在 1 fg/mL 至 1 ng/mL 的浓度范围内表现出理想的线性响应，检测限低至 0.29 fg/mL。TPE MCs 表现出的 RIM 增强电化学发光为进一步应用探索聚集态有机发光体提供了新的篇章。
