RESUMO
Convenient and highly sensitive detection of oxalate ions in body fluids is of crucial significance for disease prevention, diagnosis, and monitoring of treatment effectiveness. Establishing a simple solid-state electrochemiluminescence (ECL) sensing system for highly sensitive detection of oxalate ions is highly desirable. In this work, a solid ECL sensor was fabricated by immobilizing the commonly used emitter ruthenium(II)tris(bipyridine) (Ru(bpy)32+) on a double-layered bipolar silica nanochannel array film (bp-SNA)-modified electrode, enabling sensitive detection of oxalate ions in serum or urine samples. Cost-effective and readily available indium tin oxide (ITO) was used as the supporting electrode. Convenient fabrication of multiple negatively charged SNA (n-SNA)-modified ITO electrodes was achieved through the one-step Stöber solution growth method. Subsequently, a positive outer layer film (p-SNA) was rapidly prepared using an electrochemical-assisted self-assembly method. The double-layered bipolar silica nanochannel array film achieved stable immobilization of Ru(bpy)32+ on the electrode surface, facilitated by the electrostatic adsorption of Ru(bpy)32+ by n-SNA and the electrostatic repulsion by p-SNA. Utilizing oxalate ions as a co-reactant for Ru(bpy)32+, combined with the electrostatic enrichment of oxalate ions by p-SNA, the constructed sensor enabled highly sensitive detection of oxalate ions ranging from 1 nM to 25 µM and from 25 µM to 1 mM, with a detection limit (LOD) of 0.8 nM. The fabricated ECL sensor exhibited high selectivity and good stability, making it suitable for ECL detection of oxalate ions in serum and urine samples.