ArticleMikrochimica acta2026
A homogeneous fluorescence-electrochemiluminescence sensing platform based on EDTA-RuCOFs: ultrasensitive detection of Cu²⁺ via a chelation-quenching mechanism.
Article in Mikrochimica acta, 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
The rational design and synthesis is reported of a novel ethylenediaminetetraacetic acid (EDTA) functionalized ruthenium-based covalent organic framework (EDTA-RuCOF) and its application in constructing a homogeneous dual-mode fluorescence/electrochemiluminescence (FL-ECL) sensing platform for ultrasensitive Cu²⁺ detection. The COF was built using tris(4,4'-dicarboxybipyridine)ruthenium chloride as the luminophore and 4,4',4″-(1,3,5-triazine-2,4,6-triyl)trianiline as the structural node. EDTA moieties were subsequently anchored onto the framework through amide coupling, introducing N, N'-chelating sites within the COF framework. Unlike conventional heterogeneous sensors relying on electrode surface immobilization, the EDTA-RuCOFs are stably and homogeneously dispersed in solution, enabling truly homogeneous detection throughout the entire reaction volume. This strategy helps mitigate limitations commonly associated with interfacial sensors of interfacial sensors, significantly enhancing reaction efficiency while avoiding common drawbacks such as active-site burial, signal attenuation, and instability of modification layers. Upon selective coordination with Cu²⁺, the fluorescence and electrochemiluminescence signals of the surrounding Ru(bpy)₃²⁺ luminophores are synchronously quenched through efficient electron and energy transfer pathways, consistent with a coordination-induced "chelation-quenching" sensing process. The resulting homogeneous sensor exhibits excellent analytical performance, achieving ultralow detection limits of 2.16 pM and 263 fM for Cu²⁺ via FL and ECL modes, respectively, along with a wide linear range and high selectivity. Practical applicability was further demonstrated by accurate Cu²⁺ determination in complex real samples, including lake water, rat serum, and the traditional Chinese medicine Astragalus, with results in good agreement with those obtained by ICP-MS. Overall, this work provides a robust homogeneous dual-mode sensing strategy for trace heavy-metal detection and highlights the considerable potential of functionalized COF materials in advanced analytical and environmental monitoring applications.
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