Pan Jin-Jie, Chen Mi, Zhu Hao-Tian, Wang Ai-Jun, Yuan Pei-Xin, Feng Jiu-Ju
College of Chemistry and Materials Sciences, College of Geography and Environmental Sciences, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004, China.
College of Chemistry and Materials Sciences, College of Geography and Environmental Sciences, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004, China.
Anal Chim Acta. 2025 Oct 15;1371:344391. doi: 10.1016/j.aca.2025.344391. Epub 2025 Jul 9.
The demand for high-performance electrochemiluminescence (ECL) emitters in aqueous media continues to grow due to requirements for ultrasensitive biomedical detection. In this work, we report the synthesis of Zn (II) meso-tetra(4-carboxyphenyl) porphine (ZnTCPP) integrated with 4,4',4″-tricarboxytriphenylamine (TBA) for forming porphyrin-based hydrogen bond organic frameworks (ZnP-HOFs). The ZnP-HOFs showed strong ECL emission using KSO as coreactant, achieving a 5.85-fold amplification in ECL efficiency alternative to the ZnTCPP monomer. The enhanced mechanism was carefully discussed through electron paramagnetic resonance (EPR) and ultraviolet photoelectron spectroscopy (UPS) studies. With this advanced ECL luminophore, a "signal off-on" ECL biosensor was constructed for determining breast cancer 1 gene (BRCA1) by signal recovery after removing a black hole quencher (BHQ) linked DNA, showing a wide linear range from 1.0 pM to 0.1 μM, an ultralow limit of detection (LOD) down to 0.44 pM, and even the excellent recovery in serum sample. Thus, this work highlights the potential of HOFs-based materials in bioanalysis and establishes a universal, robust strategy for ECL biosensing applications.
由于超灵敏生物医学检测的需求，对水性介质中高性能电化学发光（ECL）发光体的需求持续增长。在这项工作中，我们报告了与4,4',4″-三羧基三苯胺（TBA）集成的锌（II）中-四（4-羧基苯基）卟啉（ZnTCPP）的合成，用于形成基于卟啉的氢键有机框架（ZnP-HOFs）。ZnP-HOFs以KSO作为共反应剂时表现出强烈的ECL发射，与ZnTCPP单体相比，ECL效率提高了5.85倍。通过电子顺磁共振（EPR）和紫外光电子能谱（UPS）研究仔细讨论了增强机制。利用这种先进的ECL发光体，构建了一种“信号关-开”ECL生物传感器，通过去除连接有黑洞猝灭剂（BHQ）的DNA后的信号恢复来测定乳腺癌1基因（BRCA1），显示出从1.0 pM到0.1 μM的宽线性范围、低至0.44 pM的超低检测限，甚至在血清样品中具有出色的回收率。因此，这项工作突出了基于HOFs的材料在生物分析中的潜力，并为ECL生物传感应用建立了一种通用、稳健的策略。
