Xing Shuyue, Liu Xuejing, Fan Dawei, Gao Zhongfeng, Ma Hongmin, Wang Huan, Wu Dan, Wei Qin
Key Laboratory of Interfacial Reaction & Sensing Analysis in Universities of Shandong, School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China.
Anal Chem. 2025 Jul 1;97(25):13248-13255. doi: 10.1021/acs.analchem.5c01270. Epub 2025 Jun 20.
In this study, chemically polymerized luminol-hydrogen-bonded organic framework (CpL-HOF) is used as the efficient luminophore and POMs@MOFs as the quencher to construct the electrochemiluminescence (ECL) sensor for the ultrasensitive detection of estriol (E3). CpL-HOF is prepared through coordination self-assembly using chemically polymerized luminol (CpL) and three active ligands. The nanoconfinement effect of CpL-HOF exhibits enhanced stability and ECL efficiency compared with the monomer. Mo-based polyoxometalates (Mo POMs) as guests are encapsulated inside a metal-organic framework (Cu-MOF) to synthesize POMs@MOFs nanocomposites with "three-in-one" functions. The distinctive host-guest interaction enhances the activity of superoxide dismutase-like (SOD-like) and catalase-like (CAT-like) enzymes, effectively eliminating reactive oxygen species (ROS). Furthermore, POMs@MOFs exhibit electron-rich redox properties, which can further eliminate ROS by valence switching. Therefore, POMs@MOFs can effectively quench the ECL signal of the CpL-HOF and improve the sensitivity of the sensor. Under optimal conditions, the sensor has a wide linear range (100 fg/mL to 200 ng/mL) and a low limit of detection (92.84 fg/mL). The sensor can be applied to the analysis of real samples, with satisfactory results. The ECL mechanism based on the synergistic interaction of the host-guest provides a theoretical foundation for constructing novel ECL sensing platforms.
在本研究中，化学聚合鲁米诺氢键有机框架（CpL-HOF）用作高效发光体，多金属氧酸盐@金属有机框架（POMs@MOFs）用作猝灭剂，构建用于超灵敏检测雌三醇（E3）的电化学发光（ECL）传感器。CpL-HOF通过化学聚合鲁米诺（CpL）与三种活性配体进行配位自组装制备而成。与单体相比，CpL-HOF的纳米限域效应表现出更高的稳定性和ECL效率。作为客体的钼基多金属氧酸盐（Mo POMs）被封装在金属有机框架（Cu-MOF）内部，以合成具有“三合一”功能的POMs@MOFs纳米复合材料。独特的主客体相互作用增强了超氧化物歧化酶样（SOD样）和过氧化氢酶样（CAT样）酶的活性，有效消除活性氧（ROS）。此外，POMs@MOFs表现出富电子的氧化还原性质，可通过价态转换进一步消除ROS。因此，POMs@MOFs可有效猝灭CpL-HOF的ECL信号，提高传感器的灵敏度。在最佳条件下，该传感器具有宽线性范围（100 fg/mL至200 ng/mL）和低检测限（92.84 fg/mL）。该传感器可应用于实际样品分析，结果令人满意。基于主客体协同相互作用的ECL机制为构建新型ECL传感平台提供了理论基础。
