Guo Jinna, Xie Mingsen, Du Peiyao, Liu Yu, Lu Xiaoquan
Tianjin Key Laboratory of Molecular Optoelectronic Science, Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, People's Republic of China.
Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, People's Republic of China.
Anal Chem. 2021 Aug 3;93(30):10619-10626. doi: 10.1021/acs.analchem.1c01891. Epub 2021 Jul 20.
Luminol, as a classical luminophore, plays a crucial role in electrochemiluminescence (ECL). However, the traditional luminol-HO ECL system suffers from the self-decomposition of HO at ambient temperature, which hinders its further application in quantitative analysis. In this work, for the first time, we developed atomically gold-supported two-dimensional VO nanobelts (Au/VO) as an advanced co-reaction promoter to speed up the reduction of dissolved oxygen to superoxide radicals (O), which react with the luminol anion radical and greatly promote the ECL emission. The ECL resonance energy transfer (ECL-RET) between the hollow manganese dioxide nanospheres and luminol results in a conspicuously decreased ECL signal response, and in the presence of glutathione (GSH), effective redox reaction between manganese dioxide and GSH restores the ECL signal. As a consequence, the designed sensor based on ECL-RET-assisted Au/VO signal amplification showed outstanding performance for "signal-on" detection of GSH in the concentration range of 10 to 10 M, and the detection limit was as low as 0.03 nM. The ECL sensor displayed excellent specificity and was successfully utilized to target GSH in real human serum samples. Importantly, this work not only highlights a powerful avenue for constructing an ultrasensitive ECL sensor for GSH but also provides some inspiration for the further design of high-performance co-reaction accelerators using the ECL technique.
鲁米诺作为一种经典的发光体,在电化学发光(ECL)中起着关键作用。然而,传统的鲁米诺-过氧化氢ECL体系在室温下存在过氧化氢的自分解问题,这阻碍了其在定量分析中的进一步应用。在这项工作中,我们首次开发了原子级金负载的二维VO纳米带(Au/VO)作为一种先进的共反应促进剂,以加速溶解氧还原为超氧自由基(O),超氧自由基与鲁米诺阴离子自由基反应并极大地促进ECL发射。中空二氧化锰纳米球与鲁米诺之间的ECL共振能量转移(ECL-RET)导致ECL信号响应显著降低,而在谷胱甘肽(GSH)存在下,二氧化锰与GSH之间的有效氧化还原反应恢复了ECL信号。因此,基于ECL-RET辅助Au/VO信号放大设计的传感器在10至10 M浓度范围内对GSH的“信号开启”检测表现出优异的性能,检测限低至0.03 nM。该ECL传感器显示出优异的特异性,并成功用于检测真实人血清样品中的GSH。重要的是,这项工作不仅突出了构建用于GSH的超灵敏ECL传感器的有效途径,还为使用ECL技术进一步设计高性能共反应促进剂提供了一些启示。