MIIT Key Laboratory of Advanced Display Materials and Devices, School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing210094, P. R. China.
School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing210094, P. R. China.
ACS Sens. 2022 Oct 28;7(10):3085-3093. doi: 10.1021/acssensors.2c01425. Epub 2022 Oct 12.
A novel electrochemiluminescence (ECL) amplification strategy was established aiming to overcome the inherent shortcomings of the current oxygen (O) coreactant ECL systems. Macrocyclic Schiff base Fe complexes were rationally designed as a novel integrated ECL emitter by iminium linkage between -(4-aminobutyl)--ethylisoluminol (ABEI) and 1,10-phenanthroline-2,9-dicarbaldehyde (PDL) and postmetalation of the macrocyclic Schiff base. Covalently combining luminophore ABEI with a catalytic center endowed the novel ECL emitter with both remarkable redox electrocatalytic properties and significantly enhanced ECL efficiency. The high content of ferrous iron and the dominantly active low-spin Fe state greatly contributed to the inherent catalytic activity for O activation. The rational modification of luminophore optimized the spatial distribution and simultaneously shortened the species transport distance of coreactant radicals generated in situ from dissolved O, resulting in significantly self-enhanced ECL efficiency. Neomycin, which posed a growing threat to aquatic biodiversity and environmental safety, as the model antibiotic was successfully detected with a detection limit of 0.21 pM (/ = 3), clarifying a promising application prospect of this new luminophore-embedded ECL amplification strategy in biological analysis and environmental monitoring.
一种新型的电致化学发光（ECL）放大策略被建立，旨在克服当前氧气（O）共反应剂 ECL 系统的固有缺点。大环席夫碱 Fe 配合物通过 -(4-氨基丁基)-乙基异鲁米诺（ABEI）和 1,10-菲咯啉-2,9-二醛（PDL）之间的亚胺键以及大环席夫碱的后金属化，被合理设计为一种新型的集成 ECL 发射器。将发光体 ABEI 与催化中心共价结合，赋予了新型 ECL 发射器显著的氧化还原电催化性能和显著增强的 ECL 效率。高铁含量和占主导地位的低自旋 Fe 态极大地促进了对 O 激活的固有催化活性。发光体的合理修饰优化了空间分布，并同时缩短了从溶解的 O 原位生成的共反应剂自由基的物质传输距离，从而显著提高了自增强的 ECL 效率。新霉素作为一种对水生生物多样性和环境安全构成越来越大威胁的模型抗生素，被成功检测到，检测限为 0.21 pM（/ = 3），这说明了这种新型发光体嵌入 ECL 放大策略在生物分析和环境监测中的应用前景广阔。
