Fu Zhixin, He Ying, Yang Guomin, Yang Jun, Yuan Ruo, Chen Shihong
Key Laboratory of Luminescence Analysis and Molecular Sensing (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, PR China.
Key Laboratory of Luminescence Analysis and Molecular Sensing (Southwest University), Ministry of Education, College of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, PR China.
Biosens Bioelectron. 2025 Dec 1;289:117887. doi: 10.1016/j.bios.2025.117887. Epub 2025 Aug 13.
3,4,9,10-perylenetetracarboxylic acid (PTCA), as a typical polycyclic aromatic hydrocarbon (PAH), has become a special electrochemiluminescence (ECL) luminophore by virtue of its high quantum yield and excellent photoelectric properties. However, its aggregation-caused quenching (ACQ) effect and high ECL potentials (usually greater than -1.5 V vs Ag/AgCl) limited its application. In this work, a dual-ligand metal-organic framework (d-MOF) with zinc ion (Zn) as the metal node and luminophore PTCA and electroactive agent carbohydrazide (CONH) as ligands was developed to address the application limitations of PTCA. The synthesis of PTCA-based MOF reduced the ACQ of PTCA. The introduction of CONH not only increased the porosity and surface area of d-MOF, but also acted as a coreaction accelerator to accelerate the reduction of persulfate ions (SO). As a result, the resulting d-MOF exhibited a strong ECL emission at a low potential of -1.1 V. Impressively, compared with single-ligand MOF (s-MOF) with PTCA alone, the ECL efficiency of d-MOF with PTCA and CONH was enhanced by 14.6 times. The d-MOF coupled toehold-mediated strand displacement (TMSD) reaction and telomerase extension of telomeric DNA strategy to achieve an ultrasensitive detection of antibiotic kanamycin (KAN) with a limit of detection of 0.24 fM. This strategy not only innovatively applied hydrazine compounds as the second ligand to reduce the ECL potential of PTCA-based MOF, but also developed a low ECL triggering potential d-MOF and created a promising platform for KAN assay.
3,4,9,10-苝四羧酸（PTCA）作为一种典型的多环芳烃（PAH），凭借其高量子产率和优异的光电性能，已成为一种特殊的电化学发光（ECL）发光体。然而，其聚集诱导猝灭（ACQ）效应和高ECL电位（相对于Ag/AgCl通常大于-1.5 V）限制了其应用。在这项工作中，开发了一种以锌离子（Zn）为金属节点、发光体PTCA和电活性试剂 carbohydrazide（CONH）为配体的双配体金属有机框架（d-MOF），以解决PTCA的应用局限性。基于PTCA的MOF的合成降低了PTCA的ACQ。CONH的引入不仅增加了d-MOF的孔隙率和表面积，还作为共反应促进剂加速过硫酸根离子（SO）的还原。结果，所得的d-MOF在-1.1 V的低电位下表现出强烈的ECL发射。令人印象深刻的是，与仅含PTCA的单配体MOF（s-MOF）相比，含PTCA和CONH的d-MOF的ECL效率提高了14.6倍。d-MOF结合了链置换介导的链置换（TMSD）反应和端粒DNA的端粒酶延伸策略，实现了对抗生素卡那霉素（KAN）的超灵敏检测，检测限为0.24 fM。该策略不仅创新地应用肼化合物作为第二配体来降低基于PTCA的MOF的ECL电位，还开发了一种低ECL触发电位的d-MOF，并为KAN检测创造了一个有前景的平台。
